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14th European Workshop on Phosphorus Chemistry

“Babeș-Bolyai” University Faculty of Chemistry and Chemical Engineering

Cluj-Napoca, ROMANIA

EWPC 14/2017

Book of Abstracts

supported by

March 20-22, 2017 Cluj-Napoca, ROMANIA

“ B a b e ș - B o l y a i ” U n i v e r s i t y , F a c u l t y o f C h e m i s t r y a n d C h e m i c a l E n g i n e e r i n g , C l u j - N a p o c a , R O M A N I A

14th European Workshop on Phosphorus Chemistry EWPC 14/2017

March 20-22, 2017

Venue: 7 Pandurilor Street, Cluj-Napoca, ROMANIA

European Workshop on Phosphorus Chemistry - EWPC 14/2017

2 0 1 7 March 20-22


Dear Participants,

Welcome to the 14th European Workshop on Phosphorus Chemistry in Cluj-Napoca

The 14th European Workshop on Phosphorus Chemistry continues continues the series of meetings held in Kaiserslautern (2004), Bonn (2005), Leipzig (2006), Zandvoort (2007), Regensburg (2008), Florence (2009), Budapest (2010), Münster (2011), Rennes (2012), Regensburg (2013), Sofia (2014), Kassel (2015) and Berlin (2016). It supports and reinforces the position of European groups within the field of phosphorus chemistry worldwide. The topics of the workshop cover all modern aspects of phosphorus chemistry in a wide range of disciplines including organic, inorganic, polymer and biomolecular chemistry as well as material science and others.

The workshop is a very good platform for intense exchange of ideas and opinions, for discussion on fundamental as well as applied aspects of contemporary phosphorus chemistry. The core of the meeting is dominated by lectures and posters of PhD students presenting their latest results. Three invited speakers, Maurizio Peruzzini (Florence, Italy), Muriel Hissler (Rennes, France) and Paul Pringle (Bristol, UK) will present the results of some of the strongest research groups in Europe. EWPC-14 will include a satellite meeting of the COST Action CM1302 - European Network on Smart Inorganic Polymers (SIPs) dedicated to the participation of SIPs members working in the field of phosphorus-based polymers.

This year we are happy to welcome more than 120 participants from 12 countries, (28 oral presentations and 62 posters). Awards for the best talks, chairpersons and posters will be given. We succeeded to keep the tradition of no registration fees for the participants due to our generous sponsors and supporters which we would like to acknowledge gratefully.

We hope you find time to combine the marvels of phosphorus chemistry with the interesting places of Cluj-Napoca, a city with rich history and culture.

On behalf of the organizing team I wish you a pleasant and informative stay in Cluj-Napoca.

Luminita Silaghi-Dumitrescu


The Organizing Committee

Prof. Luminita Silaghi Dumitrescu, Ph.D

Assoc. Prof. Gabriela Nemes, Ph.D

Assoc. Prof. Castelia Cristea, Ph.D

Assoc. Prof. Luiza Gaina, Ph.D

Assist. Raluca Septelean, Ph.D

Assist. Emese Gal, PhD

Dan Porumb, PhD

Alexandru Lupan, PhD

Noemi Deak, MSc

Eva Andrea Molnar, MSc

Lavinia Buta, MSc

Adrian Branzanic, MSc

Luana Radu, MSc


Timetable EWPC-14

Location: 7, Pandurilor Street, Babes-Bolyai University, Cluj-Napoca,

Monday, 20th March 2017

8.30–9.30 Registration

9.30–9.40 Opening Remarks

9.40–10.40 Plenary lecture (Chair: Evamarie Hey-Hawkins)

Maurizio Peruzzini (Florence, IT) PL1

10.40–11.10 Coffee break

1st Session (Chair: John Popp)

11.10–11.30 Daniel Morales Salazar (Uppsala, SE) O01

11.30–11.50 Tim Suhrbier (Rostock, DE) O02

11.50–12.10 Dirk Bockfeld (Braunschweig, DE) O03

12.10–12.30 Mocanu Olivia (Rennes, FR) O04

12.30–12.50 Abhishek Koner (Bonn, DE) O05

12.50–14.20 Lunch

2nd Session (Chair: Daniel Morales Salazar)

14.20–14.40 John Popp (Leipzig, DE) O06

14.40–15.00 Merten Lange (Muenster, DE) O07

15.00–15.20 Zsolt Kelemen (Kassel, DE) O08

15.20–15.40 Robert Konrath (St Andrews, Scotland, UK) O09

15.40–16.00 Stefan Weller (Stuttgart, DE) O10

16.00–16.20 Natalia Wojtowicz (Wroclaw, PL) O11


Tuesday, 21st March 2017

8.30–9.30 Plenary lecture (Chair: Christian Müller)

Muriel Hissler (Rennes, FR) PL2

3th Session (Chair - Andreas-Erich Seitz)

9.30–9.50 Ádám Tajti (Budapest, HU) O12

9.50–10.10 Christian Roedl (Regensburg, DE) O13

10.10–10.30 Keyhan Esfandiarfard (Uppsala, SE) O14



4th Session (Chair - Steven Giese)

11.00–11.20 Michal Talma (Wroclaw, PL) O15

11.20–11.40 Hubert Meissel (Bristol, UK) O16

11.40–12.00 Hanf Schirin (Cambridge, UK) O17

12.00–12.20 Weronika Wanat (Wroclaw, PL) O18

12.20–12.40 Botez Laurian (Amsterdam, NL) O19

12.40–13.00 Krishna Mistry (Bristol, UK) O20

13.00–15.00 Lunch and POSTER SESSION

15.00–16.20 Coffee break and POSTER SESSION

5th Session (Chair - Stephen Schulz)

16.20–16.40 Katarzyna Włodarczyk (Lublin, PL) O21

16.40–17.00 Andreas-Erich Seitz (Regensburg, DE) O22

17.00–17.20 Mustieles Irene (Paris, FR) O23

17.20–17.40 Stephen Schulz (Dresden, DE) O24

19.30 - Conference dinner at the Restaurant Casa Universitarilor, 1 Emanuel de Martonne Street

Wednesday, 22nd March

8.30–9.30 Plenary lecture (Chair: Anne-Marie Caminade)

Paul Pringle (Bristol, UK) PL3

6st Session (Chair: Mocanu Olivia)

9.30–9.50 Steven Giese (Berlin, DE) O25

9.50–10.10 Dániel Buzsáki (Budapest, HU) O26

10.10–10.30 Beil Andreas (Zurich, CH) O27

10.30–10.50 Muhammed Kanat (Istanbul, TR) O28

10.50–11.20 Coffee Break/ Jury Meeting

11.20-12.00 Award Ceremony/Presentation of EWPC-15/ Closing Remarks


2 0 1 7 March 20-22


ORAL PRESENTATIONS


2 0 1 7 March 20-22



2 0 1 7 March 20-22


P L 1

WHITE, BLACK AMD RED: PLAYING WITH ELEMENTAL PHOSPHORUS AND

TRANSITION METALS

Maurizio Peruzzini1

e-mail: [email protected]

1ICCOM – CNR, Via Madonna del Piano, 10 – 50019 Sesto Fiorentino, Italy

Department of Chemical Sciences and Technologies of Materials, DSCTM - CNR, Rome, Italy

In this communication the most recent achievements in the area of elemental

phosphorus' reactivity deriving from the authors' own research in Florence (Italy), will be

presented and discussed.

These will include: i) the activation of white phosphorus mediated by late-transition

metal complexes with particular emphasis to the unusual hydrolytic behaviour of the P4

molecule following its η1-coordination to a metal centre (Fe, Ru, Os) [1];

ii) the high pressure reactivity of red phosphorus towards water and other small

molecules [2]

and, iii) our preliminary results in exploring the chemistry of the less reactive allotrope

of the element, i.e. black phosphorus.[3]

Highlights of this work will be:

i) the presentation of the stepwise demolition by water of both mono- and

bidentatetetraphosphorus ligands in ruthenium complexes, which result in a

variety of Px fragments (x ≤ 4) like P-oxyacids, phosphanes and

hydroxyphosphanes stabilised by metal-coordination at ruthenium and,

ii) the easy access to twodimensional flakes of phosphorene (the all-P counterpart

of graphene) via a solution synthesis which avoids the use of boring and

scarcely productive scotch-tape exfoliation procedures.

Key words: White Phosphorus, Red Phosphorus, Black Phosphorus, Phosphorene, Ruthenium

References:

[1] Barbaro P., Bazzicalupi C., Peruzzini M., Seniori Costantini S., Stoppioni P.

Angew. Chem. Int. Ed. 2012, 51, 8628 – 8631 and references therein.

[2] Ceppatelli M., Bini R., Caporali M., Peruzzini M. Angew. Chem. Int. Ed. 2013, 52,

2313 –2317.

[3] Serrano-Ruiz M., Caporali M., Ienco A., Piazza V., Heun S., Peruzzini M. Adv.

Mat. Interfaces, 2016, 3, 1500441 - [http://arxiv.org/abs/1511.04330].

Acknowledgements: MP thanks all the coworkers listed in the references. Thanks are

expressed to EC through the SUSPHOS grant RFP7-PEOPLE-2012-ITN – 317404 and to the

European Research Council (ERC) under the European Union's Horizon 2020 (Grant

Agreement No. 670173) for funding the project PHOSFUN `Phosphorene functionalization:

a new platform for advanced multifunctional materials' through an ERC Advanced Grant.


2 0 1 7 March 20-22


P L 2

ADVANCES IN PHOSPHORUS BASED MOLECULAR MATERIALS

FOR OPTO-ELECTRONIC APPLICATIONS

Muriel Hissler


Institut des Sciences Chimiques de Rennes, CNRS-Université de Rennes 1, France

Since the pioneering work of Shirakawa, Heeger and McDiarmid in the 1970’s, the

interest for organic -conjugated systems has grown tremendously. Indeed organic materials

offer the possibility to process light-weight, flexible electronic devices, however, they have to

satisfy a large number of technical requirements in order to be stable and efficient in the

device. The insertion of a heteroelement into the backbone has appeared as an appealing way

to tune the properties of the materials. Heterocycles like thiophene, pyrrole, and their

derivatives are now widely used to modify chemical and physical properties of -conjugated

systems. Interestingly, while organophosphorus derivatives have been investigated for

decades, their insertion into devices has only been achieved recently. The high reactivity and

toxicity of many P-derivatives is one of the reason but the ability of chemists to stabilize and

protect the P-atom allowed the introduction of organophosphorus derivatives into opto-

electronic devices. Here, we will report on phosphorus based molecular materials: their

synthesis, their unique properties useful for organic electronic materials, and the devices that

they have been incorporated in so far. For example, we have shown that phosphorus

heterocycles (phospholes, phosphetes…) are appealing building blocks for the construction of

-conjugated systems. Effectively,

the reactivity of the P-center allows a

straightforward HOMO-LUMO gap

tuning as evidence by photophysical

and electrochemical studies. The

coordination ability of the P-center

allows unprecedented coordination-

driven assembly of -systems onto

transition metals. All these physical

properties make phosphorus

heterocycles valuable building blocks

for the development of material for

optoelectronic applications.

Keywords: Heterochemistry, Phosphorus heterocycles, Aromaticity, -systems,

Organic Optoelectronics

References:

[1] D. Joly, D.; P. A. Bouit, M. Hissler, J. Mater. Chem. C 2016, 4, 3686.

[2] M. P. Duffy, W. Delaunay, P.A. Bouit, M. Hissler, Chem. Soc. Rev. 2016, 45, 5296.

Optoelectronic Applications

OLEDs, Solar cells,

OFETs…

P

Oligomers, Polymers,

Polycycles…

Organophosphorus -conjugated systems

P-chemistry/ Heterochemistry / Organometallics


2 0 1 7 March 20-22


P L 3

REVELATIONS, EN ROUTE TO LIGANDS

CONTAINING P–O, P–C OR P–B BONDS

Paul G Pringle


University of Bristol, UK

It is difficult to overstate the importance of phosphorus(III) ligands in coordination

chemistry and homogeneous catalysis. For more than half a century, they have been at the

core of many academic discoveries and industrial applications. The reasons why research into

the development of new phosphorus(III) ligands continues unabated will be explored.

Phosphines and phosphites are ubiquitous in chemistry and the great variety in their

structures that is available is due to the numerous ways that P–C and P–O bonds can be

constructed. Here we report a series of P/Si exchange reactions that provide a way to make

chiral diphos ligands such as 1 and a new route to arylphosphites such as 2. An extension of

this exchange reaction gives ready access to borylphosphines such as 3.

The properties of ligands 1 and 3, including their applications in catalysis, will be

presented. Investigations of the mechanisms of the reactions to form 1 and 2 have revealed the

surprising role that HCl can play.


2 0 1 7 March 20-22


O 0 1

Functional small-molecules & polymers

containing P=C and As=C bonds as hybrid

π-conjugated materials

Daniel Morales Salazar1, Edgar Mijangos1, Sonja Pullen1, Ming Gao2, and

Andreas Orthaber1

[email protected]

1Department of Chemistry, Ångström Laboratories, Molecular Inorganic Chemistry,

Uppsala University, Box 523, 75120 Uppsala, Sweden 2Department of Chemistry, Ångström Laboratories, Polymer Chemistry,

Uppsala University, Box 523, 75120 Uppsala, Sweden

The incorporation of heavy main group elements (e.g. Si, Ge, P, As, S, Se, etc.) into π-

conjugated molecular and polymeric systems has received great attention due to the diverse

bonding and innate properties offered by these atoms, which ultimately have an impact in all

physical and chemical properties of the resulting materials. These “hybrids” are studied as

alternatives for organic field effect transistors (OFETs), solar cells, nonlinear optical devices,

electrochromic devices, and other stimuli-responsive materials.1,2 Inhere, stable phospha- (2a)

and arsaalkene (2b) were used to synthesize polymers containing unsaturated P=C (poly-2a)

and A=C (poly-2b) moieties. The incorporation of the heteroatom-carbon double bonded unit

in a planar fashion with respect to the π-scaffold efficiently perturbed the optoelectronics and

solid state features of both monomers and polymers; both types of polymer films displayed

reversible electrochromic behaviour; additionally, the accessibility of a lone pair was

confirmed by post-functionalization of 2a and poly-2a with Au(I) ions, which significantly

perturbed the optoelectronics of the systems. To the best of our knowledge, this is the first

example of a polymer containing arsenic-carbon double bonds.3 We acknowledge the

European COST network on Smart Inorganic Polymers (SIPs, CM1302).

Figure 1. a) SEM of poly-2b b) UV-Vis-NIR of phosphaalkenes c) DFT LUMO of tetramer model of 2b Key words: pnictogen, phosphaalkene, hybrid-polymers, heavy-main-group, electrochromism

References: [1] M. A. Shameem and A. Orthaber, Chem. Eur. J. 22 (2016) 10718–10735.

[2] J. P. Green, Y. Han, R. Kilmurray, M. A. McLachlan, T. D. Anthopoulos

and M. Heeney, Angew. Chem., Int. Ed 55 (2016) 7148–7151.

[3] D. Morales Salazar, E. Mijangos, S. Pullen, M. Gao, and A. Orthaber, Chem. Commun.

10.1039/C6CC08736A (2016).

400 500 600 700 800

0.00

0.25

0.50

0.75

1.00

500 600 700 8000.00

0.01

0.02

0.03

2a

2a-AuCl

poly-2aAuCl

poly-2a

No

rma

lize

d A

bs

orb

an

ce

(A

U)

Wavelength (nm)


2 0 1 7 March 20-22

“ B abe ș - B o l y a i ” U n i v e r s i t y , F a c u l t y o f C h e m i s t r y a n d C h e m i c a l E n g i n e e r i n g , C l u j - N a p o c a , R O M A N I A

O 0 2

Dichloro-cycloazatriphosphane – a novel NP3 ring system

Tim Suhrbier1, Jonas Bresien1, Alexander Hinz2, Axel Schulz1,3, Alexander Villinger1 [email protected], [email protected]

1Institut für Chemie, Abteilung Anorganische Chemie, Universität Rostock, Albert-Einstein-Straße 3a, 18059 Rostock, Germany.

2Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, Great Britain.

3Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Straße 29a, 18059 Rostock, Germany.

Ring systems based on group 15 elements (pnictogens) have been in the focus of

chemical research for almost 150 years.[1] Especially, N2P2 cycles of the type A (Scheme 1, top) have been thoroughly investigated over the past few decades.[2] More recently, the homologous P4 ring systems (B) were studied, particularly with respect to their reactivity.[3] However, little is known about four membered cycles containing three phosphorus atoms and one nitrogen atom (NP3).[4] In the light of these results, we are currently investigating ring systems of the type C, a formal blend of structures A and B.

PN

PN

X

R R

X A

PP

PP

X

R R

X

PP

PN

X

R R

XB C

RP

PN

R

H

1

n-BuLiPCl3 R

PP

NR

PCl2 PP

PN

Cl

R R

Cl2 3 Scheme 1. Top: Ring systems of type A, B and C (R = C or Si based substituent, X = (pseudo)halogen). Bottom: Synthesis of 2 and 3 (R = Mes* = 2,4,6-tri-tert-butylphenyl).

Starting from Mes*PPN(H)Mes* (1),[5] it was possible to generate the novel diphosphene Mes*PPN(PCl2)Mes* (2, Scheme 1, bottom), a formal open-chain isomer of the desired ring system Mes*2NP3Cl2 (3). In polar solvents, compound 2 can be isomerized to the ring system 3, which constitutes an unprecedented dichloro-cycloazatriphosphane.

Key words: cycloazatriphosphane, ring system, isomerization, diphosphene, NP chemistry References: [1] a) H. Köhler, A. Michaelis, Ber. Dtsch. Chem. Ges. 10 (1877) 807–814; b) A. Michaelis,

G. Schroeter, Ber. Dtsch. Chem. Ges. 27 (1894) 490–497. [2] G. He, O. Shynkaruk, M. W. Lui, E. Rivard, Chem. Rev. 114 (2014) 7815–7880. [3] J. Bresien, C. Hering, A. Schulz, A. Villinger, Chem. Eur. J. 20 (2014) 12607–12615. [4] a) E. Niecke, R. Rüger, B. Krebs, M. Dartmann, Angew. Chem. 95 (1983) 570–571; b) D.

Gudat, M. Link, G. Schröder, Magn. Reson. Chem. 33 (1995) 59–65. [5] E. Niecke, B. Kramer, M. Nieger, Organometallics 10 (1991) 10–11.


2 0 1 7 March 20-22


O 0 3

FROM NHC-PHOSPHINIDENES TO NEUTRAL PHOSPHINATES AND THEIR HEAVIER HOMOLOGUES

Dirk Bockfeld1, Matthias Tamm1

e-mail: [email protected] 1Institut für Anorganische und Analytische Chemie,

Technische Universität Braunschweig, 38106 Braunschweig, Germany

Phosphinidenes (P-R) represent a highly reactive class of low-valent phosphorus compounds. Free phosphinidenes were only studied at cryogenic temperatures and in the gas phase until last year, the first free phosphinophosphinidene was reported by Bertrand.[1] N-heterocyclic carbene (NHC) stabilized phosphinidenes were first introduced by Arduengo et al. back in 1997.[2] Recently, Bertrand et al. prepared a series of different NHC-phosphinidenes.[3] Shortly after that the first NHC-phosphinidene supported transition metal complexes were reported.[4] Arising from our groups long-standing interest in NHC-imine and NHC-iminato ligands we started exploring the coordination chemistry of these phosphorus analogues which represent a promising new class of strong electron donating ancillary ligands in homogeneous catalysis.[5]

N

NP

2 E

N

NP

EE

N

NP

EE

A B

E = O, S, Se

We also started exploring the reactivity of NHC phosphinidenes towards main group elements. The oxidation of these low-valent phosphorus species with chalcogens yielded zwitterionic phosphinates, phosphinodithioates and phosphinodiselenoates respectively (A). In this contribution, the reactivity of NHC-phosphinidenes towards group 16 elements and recent advances in the coordination chemistry of these ligands will be discussed. Key words: NHC-Phosphinidenes, Phosphaalkenes, Phosphinates, Chalcogens References: [1] L. Liu, D. A. Ruiz, D. Munz, G. Bertrand, Chem 1 (2016), 147–153. [2] A. J. Arduengo, III, H. V. R. Dias, J. C. Calabrese, Chem. Lett. (1997), 143–144. [3] O. Back, M. Henry-Ellinger, C. D. Martin, D. Martin, G. Bertrand, Angew. Chem. Int. Ed. 52 (2013), 2939–2943. [4] a) T. G. Larocque, G. G. Lavoie, New J. Chem. 38 (2014), 499–502. b) V. A. K. Adiraju, M. Yousufuddin, H. V. R. Dias, Dalton Trans. 44 (2015), 4449–4454. [5] a) A. Doddi, D. Bockfeld, A. Nasr, T. Bannenberg, P. G. Jones and M. Tamm, Chem. Eur. J. 21 (2015), 16178–16189. b) D. Bockfeld, A. Doddi, P. G. Jones, M. Tamm, Eur. J. Inorg. Chem. (2016), 3704–3712.


2 0 1 7 March 20-22


O 0 4

PAHs. FUSED HETEROLES

O. A. Mocanu1, R. Szűcs2, L. Nyulàszi2, P.-A. Bouit1, M Hissler1 e-mail: [email protected]

1UMR 6226, Institut des Sciences Chimiques de Rennes, CNRS-Univ. de Rennes 1, Rennes, France 2 Departlent of Inorganic Chemistry, Budapest University of Technology and Economics, H-1521

Budapest, Hungary

Polycyclic Aromatic Hydrocarbons (PAHs) like benzocoronenes or graphene

nanoribbons (GNRs) have great potential for the development of efficient opto-electronic

devices (OSCs, OFET, etc) in the field of plastic electronics.1 Their bandgap and

supramolecular assemblies can be tuned trough size control of the π-system and side chains.2

An alternative strategy involves the incorporation of six or five-membered rings heteroatoms

such as N, S or B within the conjugated backbones of PAHs.3

Recently, planar P-containing PAHs featuring four to eight condensed rings were

developed by our research group with modest yields. Chemical modification on P allows the

tuning of the phisico-chemical properties of PAHs.4

In this contribution an alternative synthetic approach based on catalytic methods for

introduction of P and Si rings in PAHs (Scheme 1: A, B, C, D ) will be reported.5

Scheme 1: P and Si-containing PAHs obtained by catalytic method

These complexes have been carefully characterized by NMR spectroscopy and single

crystal X-ray diffraction. The optical and electrochemical properties of the PAHs have been

studied compared with theoretical models. Insertion into optoelectronic devices is envisaged

on the basis of these data.

Key words: π-conjugated systems, PAHs, optical and electronical properties,

heterochemistry

References: [1] M. Wadson, K. Müllen et al., Chem. Rev., 101, (2001), 1267-1299.

[2] X. Feng, K. Müllen et al., Adv. Mater., 22, (2010), 3634-3649.

[3] D. J. Gregg, S. Draper et al., J. Am. Chem. Soc., 124, (2002), 3486-3487; S. Saito, K. Matsuo et al.,

J. Am. Chem. Soc., 134, (2012), 9130-9133; X. Feng, K. Müllen et al., J. Am. Chem. Soc, 134, (2012),

17869-17872

[4] M. Hissler, R. Réau et al., J. Am. Chem. Soc., 134, (2012), 6524-6527; L. Nyulàszi, M. Hissler et al.

Dalton Trans., 45, (2016), 1896-1903.

[5] T. Mamoru, C. Naoto et al., Angew. Chem. Int. Ed., 52, (2013), 11892-11895;T. Kazukahiko, K.

Yoichiro et al., J. Am. Chem. Soc., (2010), 132, 14324-14326.

D C B A


2 0 1 7 March 20-22


O 0 5

IMIDAZOLE-2-THIONE-BASED ELCTRON-RICH 1,4-

DIPHOSPHININES

Abhishek Koner1, Zsolt Kelemen2, László Nyulászi2*, Rainer Streubel1*


1Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn, Gerhard Domagk-Str.1, 53121 Bonn, Germany

2Department of Inorganic and Analytical Chemistry, Budapest University of Technology and

Economics, Szt Gellert ter 4, 1111 Budapest, Hungary

Investigations on tetrakis(trifluoromethyl)-13,43-diphosphinine[1] by Kobayashi et

al. have demonstrated a great diversity in cycloaddition chemistry[2-3] using freshly prepared

solutions, only. But isolation and structural characterization of this electron-poor 1,4-diphos-

phinine derivative was not possible.

Herein, we present investigations on imidazole-2-thione-based tricyclic 13,43-di-

phosphinines III (Scheme),[4] obtained via reduction of II using various reagents and condi-

tions. Compounds II were easily synthesized from tricyclic 1,4-dihydro-1,4-diphosphinines I

and PCl3 using -bond metathesis resulting in P-N bond cleavage. Compounds III are ex-

tremely air and moisture sensitive in solution, but robust as solids. NMR studies and X-ray

structures of I-III will be discussed in detail along with their synthesis and reactivity. Based

on DFT calculations bonding, UV/vis and electrochemical properties and reactivity can be

explained.

Keywords: 1,4-dihydro-1,4-diphosphinine, 1,4-diphosphinine References: [1] Y. Kobayashi, I. Kumadaki, A. Ohsawa, W. Hamana, Tetrahedron Lett. 1976, 3715.

[2] Y. Kobayashi, W. Hamana, S. Fujino, A. Ohsawa, I. Kumadaki, J. Am. Chem. Soc. 1980,

102, 252.

[3] Y. Kobayashi, S. Fujino, J. Kumadaki, J. Am. Chem. Soc. 1981, 103, 2465.

[4] A. Koner, G. Pfeifer, Z. Kelemen, G. Schnakenburg, L. Nyuászi, T. Sasamori, R. Streubel

submitted.

mailto:[email protected]


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O 0 6

P-Stereogenic Ferrocenyl Phosphines as Novel Ligands for Asymmetric Redox-Switchable Catalysis

John Popp1, Anne-Marie Caminade2, Evamarie Hey-Hawkins1

e-mail: john.popp@uni-leipzig 1 Leipzig University, Faculty of Chemistry and Mineralogy, Institute of Inorganic

Chemistry, Johannisallee 29, 04103 Leipzig, Germany 2 CNRS, Laboratoire de Chimie de Coordination, 205 route de Narbonne, BP 44099,

31077 Toulouse Cedex 4, France

In recent catalyst development, the attention turned to homogeneous catalysts whose activity in different chemical processes can be switched by an external stimulus. Recently, our group reported on the redox control of a catalytic process, which also corroborates the power of dendritic structures in homogeneous catalysis.[1] We now have focused on introducing a P-stereogenic phosphine suitable for asymmetric induction to employ this ligand system also for homogeneous asymmetric transformations.

Employing JUGÉ’S ephedrine-based method,[2] several P-stereogenic monodentate ferrocenyl phosphines were synthesised with high enantiomeric excess (>95% ee in all cases). Their complexation behaviour with ruthenium(II) and rhodium(I), using [{(η6-p-cym)RuCl(μ-Cl)}2] (p-cym = 1-Me-4-iPrC6H4) and [{Rh(μ-Cl)(COD)}2] (COD = 1,5-cyclooctadiene) as suitable precursors, was studied. The anchoring group in the 1' position of the ferrocene derivatives allows furthermore the grafting of these P-stereogenic ferrocenyl phosphines on the surface of phosphorus-containing dendrimers developed by the research group of CAMINADE.[3]

Consequently, the obtained P-stereogenic dendritic ferrocenyl phosphines will now be applied as ligands in asymmetric redox-switchable transition metal catalysis.

Keywords: P-Stereogenity, Phosphines, Ferrocene, Catalysis, Dendrimers

References: [1] P. Neumann, H. Dib, A.-M. Caminade, E. Hey-Hawkins, Angew. Chem. 127 (2015) 316–319; Angew. Chem. Int. Ed. 54 (2015) 311–314. [2] S. Jugé, M. Stephan, J. A. Laffitte, J. P. Genet, Tetrahedron Lett. 31 (1990) 6357–6360. [3] N. Launay, A.-M. Caminade, J. P. Majoral, J. Organomet. Chem. 529 (1997) 51–58.


2 0 1 7

March 20-22


O07

AN AL/P BASED FRUSTRATED LEWIS-PAIR – SYNTHESIS OF A GRIGNARD DERIVATIVE AND GENERATION OF GA/P AND IN/P BASED FLPS

Merten Lange, Jana Backs and Werner Uhl*

[email protected]

IAAC, Westfälische Wilhelms-Universität Münster, Germany

Frustrated LEWIS Pairs (FLPs) have basic donor and acidic acceptor sites in close proximity. They are of great interest for the dipolar activation or coordination of small molecules. The geminal, sterically shielded aluminum and phosphorus based FLP 1 is obtained by a facile route via hydroalumination of an alkynylphosphine and shows a high reactivity towards small molecules such as carbon dioxide [1] and alkali metal hydrides [2]. The reaction of FLP 1 with phenylmagnesium chloride yields the unique GRIGNARD reagent 2 via transmetallation. Compound 2 is a highly interesting starting material for the synthesis of the new Ga/P and In/P based Frustrated LEWIS Pairs 3 and 4 [3].

PhMgClMes2P Mg

Ph

Cl

(THF)2

Mes2P AltBu2

Ph

tBu2GaCl

1

2

3

4

Mes2P GatBu2

Ph

THF

Mes2P

In

Ph Cl Ph

PMes2

InCl3

Figure 1: Synthesis of the In/P and Ga/P based FLPs 3 and 4.

The FLP 1 is a very effective two-electron reductant and its reaction with enones and an ynone at room temperature yielded the corresponding enol and allene adducts 5 and 6. Heating a solution of the allene 6 lead to an unprecedented rearrangement by C-H bond activation, C-C bond formation and migration of a phenyl substituent to afford the unique, tricyclic adduct 7. FLP 1 is well suited for the formation of unusual organic skeletons.

Mes2P AltBu2

Ph

1

O

Mes2P

O

AltBu2

PhPh

O

Ph P

O

AltBu2

Ph

Ph Ph

MesMes2P

CO

AltBu2

Ph

Ph

Ph∆

5 6 7 Figure 2: Synthesis of adducts 5 to 7.

References: [1] C. Appelt, H. Westenberg, F. Bertini, A. W. Ehlers, J. C. Slootweg, K. Lammertsma, W. Uhl, Angew. Chem. Int. Ed. 2011, 50, 3925. [2] C. Appelt, J. C. Slootweg, K. Lammertsma, W. Uhl, Angew. Chem. Int. Ed., 2012, 51, 5911. [3] J. Backs, M. Lange, J. Possart, A. Wollschläger, C. Mück-Lichtenfeld, W. Uhl, Angew. Chem., 2017, accepted.


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March 20-22


O 0 8

Synthesis and theoretical investigation of phosphorus containing [3]ferrocenophanes

Zsolt Kelemen1,2, Denis Kargin1, Stefan Borucki1 László Nyulászi2*, Rudolf Pietschnig1* e-mail: [email protected]

1Universität Kassel, Institut für Chemie und CINSAT, Heinrich-Plett-Str.40, 34132 Kassel, Germany 2Budapest University of Economy and Technology, Department of Inorganic and Analytical

Chemistry Szent Gellért tér 4 H-1111, Budapest, Hungary

Phosphorus containing [n]ferrocenophanes (n=1,2,3) are an interesting class of ferrocene containing compounds. Although, a few phospha-[1]ferrocenophanes,1 diphospha-[2]ferrocenophanes2 and triphospha-[3]ferrocenophanes3 are known, the chemistry of these attractive molecules have been not fully explored yet.

P

P

R

R

Fe

Scheme 1: The investigated [3]ferrocenophanes

Herein we report the synthesis and characterization of new [3]ferrocenophanes (Scheme 1).4 Since the phosphanyl units serve as stereogenic centers the possible stereochemistry will be discussed, the relative stabilities of the isomers were investigated by DFT calculations as well. The redoxchemistry of these compounds were investigated by cyclic voltammetric measurements, which were amended by DFT calculations. Furthermore possible Fe-E (E=SiX2 PX) interaction is also disputed. The stability of the analogue subvalent compounds (E=Si: P+) was determined by DFT calculations and the synthesis of them were also attempted.

We gratefully acknowledge financial support by the following programs and institutions: Deutsche Forschungsgemeinschaft and ERA Chemistry (PI 353/8-1 PI 353/9-1), OTKA K 105417, COST action CM1302 “SIPs”.

Key words: [3]ferrocenophanes, stereo isomers, DFT calculations References: [1] C. H. Honeyman, I Manners, Organometallics 1995, 14, 5503

[2] a) C. Moser, R. Pietschnig, Chem. Eur. J. 2009, 15, 12589, b) Y. Tanimoto, T.Mizuta, J. Organomet. Chem. 2012. 713, 80.

[3] A. G Osborne, M. A. Mazid, J. Organomet. Chem. 1993, 453, 117.

[4] D. Kargin, Z. Kelemen, K. Krekic, M. Maurer, C. Bruhn, L. Nyulaszi, R.

Pietschnig Dalton Trans. 2016, 45, 2180-2189.


2 0 1 7 March 20-22


O 0 9

SOLID-PHASE SYNTHESIS AND APPLICATION OF SUPPORTED PHOSPHORUS LIGAND LIBRARIES

Robert Konrath1, Frank J. L. Heutz1, Paul C. J. Kamer1*

e-mail: [email protected] 1 School of Chemistry, University of St Andrews, St Andrews, United Kingdom

Despite the advances in rational design of highly selective phosphorus-based ligands in (asymmetric) homogeneous catalysis, synthetic approaches through trial-and-error remain the most common methodologies for catalyst optimization. There is, however, still a lack of efficient combinatorial methods enabling the synthesis and screening of chiral phosphorus ligand libraries.[1]

Solid-phase synthesis (SPS) offers a useful tool for a stepwise ligand build-up by employing insoluble (in-)organic supports. This technique enables simplified purification procedures, often requiring easy filtration steps only. Systematic variation of building blocks can lead to facile access towards large supported phosphorus ligand libraries. When employed in a catalytic reaction, this approach can facilitate catalyst recovery and recycling. Recently, the successful SPS of heterobidentate phosphorus ligands, such as supported phosphine-phosphite ligands, and their application in asymmetric hydrogenation has been demonstrated within the Kamer group.[2]

Moreover, supported tridentate PNN ligands were successfully employed in the hydrogenation of esters under very mild conditions.[3] Here we report on the diversification of a supported phosphine-phosphite ligand library towards chiral C2 backbones using the SPS approach in a combinatorial fashion (see scheme).

PR1

H

a) LDA

b)

c) H+

PR1

*

R2OH

O *

R2

A

PR1

*

R2O

P(R3)2

B C

n

n = 0,1

n n

PClO

O

37 examples Furthermore, the library was employed in the Rh-catalyzed asymmetric hydrogenation of three benchmark substrates and catalyst recycling was studied under batch and flow conditions. The versatility of the SPS approach is demonstrated by the discovery of a modular access towards supported (chiral) tridentate PNP ligands.

Key words: Solid-phase-synthesis, Catalyst immobilization, Combinatorial chemistry, Catalyst Recycling References: [1] P. E. Goudriaan et al., Eur. J. Inorg. Chem. (2008), 2939-2958. [2] F. J. L. Heutz, P. C. J. Kamer, Dalton Trans. 45 (2016), 2116-2123. [3] F. J. L. Heutz et al., ChemCatChem, 8 (2016), 1896-1900.


2 0 1 7 March 20-22


O 1 0

SYNTHESIS AND REACTIVITY OF 1,1'-FERROCENYL-DIAMINO-PHOSPHANE

Stefan Weller1, Simon Schlindwein1, Rudolf Pietschnig2, László Nyulászi3, Dietrich Gudat1 e-mail: [email protected]

1Institute of Inorganic Chemistry, University of Stuttgart, Pfaffenwaldring 55, GER-70569 Stuttgart 2Institute of Chemistry, University of Kassel, Heinrich-Plett-Straße 40, GER-34132 Kassel

3Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Szt. Gellért tér 4, HUN-1521 Budapest

The chemical abilities of N-heterocyclic phosphanes with saturated and unsaturated backbones are well known[1], while diaza-phospha-ferrocenophanes[2], which can be regarded as structural analogues, are nearly unknown. In relation to our studies[3] on such electron rich diaminophosphanes[4], we are interested in the reactivity of these ferrocene-containing phosphanes, which offer a possibility to observe an interaction between the phosphorus center and the ferrocene backbone for intramolecular electron transfer processes.

The reaction of neopentyl-substituded diamino-ferrocene 1 with trichlorophosphine give a bis-chlorophosphane 2, which can be reductive coupled to a tetraphosphetane 3 or transfered to the desired ferrocenophane 4. This chloro-diaza-phospha-ferrocenophane can be converted to a phosphenium cation 5 or to a diaza-phospha-ferrocenophane 6. The conditions of these reactions, and reactivity studies of these products, will be discussed.

FeNH

NH

Np

NpFe

N

N

Np

Np

PCl2

PCl2 FeN

N

Np

P

Np

P FeN

N

Np

P

Np

P

FeN

N

Np

PCl

Np

FeN

N

Np

PH

Np

FeN

N

Np

P

Np

[AlCl4]

1 2 3

4 56 Key words: Diaza-phospha-ferrocenophanes, N-heterocyclic phosphanes References: [1] D. Gudat, Dalton Trans. 45 (2016) 5896–5907

[2] B. Wrackmeyer, E. V. Klimkina, W. Milius, Z. Naturforsch. 64b (2009) 1401-1412 b) B. Wrackmeyer, E. V. Klimkina, W. Milius, Z. Anorg. Allg. Chem. 636(5) (2010) 784-794 [3] a) D. Förster, I. Hartenbach, M. Nieger, D. Gudat, Z. Naturforsch. 67b (2012) 765-773 b) O. Puntigam, D. Förster, N.A. Giffin, S. Burck, J. Bender, F. Ehret, A.D. Hendsbee, M. Nieger, J.D. Masuda, D. Gudat, Eur. J. Inorg. Chem. 2013(12) (2013) 2041-2050 [4] a) J.P. Bezombes, P.B. Hitchcock, M.F. Lappert, J.E. Nycz, Dalton Trans. 4 (2004) 499-501 b) L. McInnes, K. Müther, V. Naseri, J.M. Rawson, D.S. Wright, Chem. Commun. 13 (2009) 1691-1693


2 0 1 7 March 20-22


O 1 1

PHOSPHONYLATION OF HETEROAROMATIC LITHIUM REAGENTS AS A GENERAL ROUTE FOR HETEROAROMATIC PHOSPHONATES

Natalia Wojtowicz1, Ewa Chmielewska1

e-mail: [email protected] 1Department of Bioorganic Chemistry, Faculty of Chemistry, Wroclaw University of Science

and Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland

Phosphonates are important class of compounds in medicinal chemistry. [1,2,3] However, the remarkable potential of these compounds is yet to be fully explored. Synthesis of heteroaromatic phosphonates is complicated and requires elaboration of new methods of general value.[4] This paper presents a synthesis using phosphonylation of lithium heteroaromates as an alternative to already described methods. A procedure of single-step synthesis was employed composed by consecutive reactions: lithiation of the 2-position of heteroaromate with n-butyllithium, followed by electrophilic attack of diethyl chlorophosphite, then oxidation using hydrogen peroxide and hydrolysis with bromotrimethylsilane (Fig.). For some substrates (e.g. benzimidazole) it was required to introduce a protecting group on the nitrogen atom. In those cases, two equivalents of n-butyllithium were used. Analysis of the results has shown that the method of synthesis using lithium reagent is effective and efficient. Moreover, the procedure is not very complicated and the substrates are easily accessible. Obtained compounds have been supplied to Institute of Immunology and Experimental Therapy Polish Academy of Sciences for anticancer studies using call lines: MCF-7 of human breast cancer and PC-3 of human prostate cancer.

Figure General reaction of phosphonylation

Key words: phosphonates, lithium reagents, heteroaromate References: [1] A. Schwanke, C. Murruzzu, B.Zdrazil, R. Zuhse, M. Natek, M. Holtje, H.C. Körting, Int. J. Pharmaceut. 397 (2010) 9-18 [2] L. Gong, R.B. Altman, T.E. Klein, Pharmacogenet Genomics 21 (2011) 50-53 [3] C.J. Leung, J. Park, J.W. De Schutter, M. Sebag, A.M. Berghuis, Y.S. Tsantrizos, J. Med. Chem. 56 (2013) 7939-7950 [4] M. Prokopowicz, P. Mlynarz, P. Kafarski, Wiad. Chem. 64 (2010) 1-22


2 0 1 7 March 20-22


O 1 2

MICROWAVE-ASSISTED SYNTHESIS OF AMINOPHOSPHONATE AND (AMINOMETHYLENE)BISPHOSPHONATE DERIVATIVES

Ádám Tajti1, Anna Ádám1, Dorottya Kalocsai1, Nóra Tóth1, Katalin Ladányi-Pára1, György

Keglevich1 and Erika Bálint2

e-mail: [email protected] 1Department of Organic Chemistry and Technology,

Budapest University of Technology and Economics, 1111 Budapest, Hungary 2MTA-BME Research Group for Organic Chemical Technology, 1111 Budapest, Hungary

α-Aminophosphonates may be considered as the P-analogues of α-amino acids. Due to this similarity they are of potential bioactivity [1]. We elaborated a solvent- and catalyst-free microwave(MW)-assisted Kabachnik-Fields condensation giving α-aminophosphonate derivatives (1) and the corresponding bis compounds (2). (Aminomethylene)bisphosphonate derivatives (3), another scaffold of bioactive compounds, were synthesized by the three-component condensation of an amine, an orthoformate and a dialkyl phosphite or secondary phosphine oxide [2].

NH +

N CH2 PO

PZ1

Z2 H

O

Z1, Z2= RO, Ph

NCH2

CH2 P

P

O

O

Y1

MW

(CH2O)n

Y1= alkyl or arylY2= H, alkyl

Y1

Y2

Y1

Y2

Z1

Z2

Z1

Z2

Z1

Z212

N CHHC(OR)3

PZ2

PZ2

O

O

Y1

Y2

3 We also studied the MW-assisted Pudovik reaction involving the addition of different

>P(O)H reagents, such as dialkyl phosphites or diphenylphosphine oxide to imines (4) [3].

MWCHHN PY

O Z

Z

Y'

C

Y'

N HY

no solvent

4 5

Z= MeO, EtO, BuO, BnO, Ph

Z2P(O)H

Beside other transformations, the Pudovik reaction was also investigated in a

continuous flow MW reactor. Keywords: microwave, α-aminophosphonates, (aminomethylene)bisphosphonates,

Pudovik addition, continuous flow MW reactor

References: [1] G. Keglevich, E. Bálint, Molecules 17 (2012) 12821–12835. [2] E. Bálint, Á. Tajti, A. Dzielak, G. Hägele, G. Keglevich, Beilstein J. Org. Chem. 12 (2016)

1493–1502. [3] E. Bálint, Á. Tajti, A. Ádám, I. Csontos, K. Karaghiosoff, M. Czugler, P. Ábrányi-Balogh,

G. Keglevich, Beilstein J. Org. Chem. 13 (2017) 76–86.


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O 1 3

Reactivity of a Silyl Substituted Bis(1,3-diphosphacyclobutadiene)cobalt Complex toward C−O Bonds and Late Transition Metal Cations

Christian Roedl, Robert Wolf


University of Regensburg, Institute of Inorganic Chemistry, Universitätsstraße 31, 93040 Regensburg, Germany

Bis(1,3-diphosphacyclobutadiene)cobaltate anions [Co(η4-P2C2R2)2]− are readily accessible by reacting phosphaalkynes with the “Co−“ source [Co(anthracene)2]−.[1] Oligonuclear complexes and supramolecular coordination compounds are formed by coordination of the phosphorus atoms to metal cations. In previous work, we studied the coordination properties of these sandwich anions toward coinage metal as well as 3d metal cations.[2-4]

Here, we present an extension of these studies using the silyl substituted compound 1 as starting material. The P−Si bond of 1 readily reacts with C−O single and double bonds. Another feature of 1 is the formation of oligonuclear compounds 3-5 by dehalosilylation of group 8, 9 and 12 metal chlorides.

PP

P

CoP

tBu

tButBu

tBu

1

Me3Si

Me3SiOR +n

2a (n=0)2b (n=1)

2c

2d

n = 3

P PtBu

tBu

P P

tBu

tBuCo

Ru

Ru

ClClRu

- Me3SiCl

0.5 HgCl2

PP

CotBu

tBu

PPtBu

tBu

P P

Co tBu

tBu

P PtBu

tBu

Hg0.5

5

3

0.75[Cp*RuCl]4

- Me3SiCl

- Me3SiCl

0.5 [RhCl(cod)]2

Rh

4

PP

P

CoP

tBu

tButBu

tBu

Cp*

Cp*

Cp*ether

lactone

epoxide

Me3SiO

P

[Co]P

tBu

tBu

P

[Co]P

tBu

tBu

P

[Co]P

tBu

tBu

n

O

Me3SiOPh

Key words: Diphosphacyclobutadiene, Cobalt, Insertion, Dehalosilylation

References: [1] R. Wolf, A. W. Ehlers, J. C. Slootweg, M. Lutz, D. Gudat, M. Hunger, A. L. Spek, K. Lammertsma, Angew. Chem. Int. Ed. 47 (2008) 4584–4587. [2] Review: A. Chirila, R. Wolf, J. C. Slootweg, K. Lammertsma, Coord. Chem. Rev. 270 (2014) 57–74. [3] a) J. Malberg, T. Wiegand, H. Eckert, M. Bodensteiner, R. Wolf, Chem. Eur. J. 19 (2013) 2356-2369; b) J. Malberg, T. Wiegand, H. Eckert, M. Bodensteiner, R. Wolf, Eur. J. Inorg. Chem. 2014 (2014) 1638–1651; c) J. Malberg, M. Bodensteiner, D. Paul, T. Wiegand, H. Eckert, R. Wolf, Angew. Chem. Int. Ed. 53 (2014) 2771–2775. [4] C. Rödl, R. Wolf, Eur. J. Inorg. Chem. 2016 (2016) 736-742.


2 0 1 7 March 20-22


O 1 4

A New Entry to C=C formation: Facile Stereo-selective Coupling of Aldehydes to E-Alkenes

Keyhan Esfandiarfard1, Juri Mai1, Sascha Ott1*

[email protected]

1Department of Chemistry – Ångström Laboratory, Box 523, 75120 Uppsala, Sweden

A new methodology leading to C=C has been introduced; an unprecedented reaction which gives E-alkene products selectively from feedstock aldehydes.

Reductive homocoupling of aldehydes as well as coupling of two different aldehydes have been accomplished affording the corresponding E-alkenes selectively. The latter is of great importance and an improvement to McMurry coupling[1] which gives a statistical mixture when two different aldehydes are used. The reaction is free of transition metal and occurs in few minutes under mild conditions. A phosphanylphosphonate[2] is the reagent which transforms the first aldehyde to a phosphaalkene intermediate. The phosphaalkene is then activated by hydroxide and reacts further with the second aldehyde in a Wittig-type reaction to form the C=C bond. It is noteworthy that such type of reactivity is not restricted to use phosphanylphosphonates (i.e. phospha-HWE reaction) for the first part of the reaction sequence and some of the various ways of making P=C bonds could potentially be utilized; a hypothesis that leaves space for future investigations and plausible modifications.

Key words: stereo-selective, reductive coupling, E-alkene, phosphanylphosphonate

Acknowledgments: Swedish Research Council is gratefuly acknowledged for the financial support. References: [1] J. E. McMurry, Chem. Rev. 89 (1989), 1513-1524. [2] K. Esfandiarfard, A. I. Arkhypchuk, A. Orthaber, S. Ott, Dalton Trans. 45 (2016), 2201-2207.


2 0 1 7 March 20-22


O 1 5

SYNTHESIS OF PHOSPHINODEHYDROPEPTIDES AND MOLECULAR MODELING OF INTERACTIONS IN THE ACTIVE

SITES OF METALLOAMINOPEPTIDASES

Michał Talma, Artur Mucha e-mail: [email protected]

Department of Bioorganic Chemistry, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław

Phosphinopeptides and their derivatives are good inhibitors of metalloproteases, the

enzymes that use metal cations to catalyze the hydrolysis of the peptide bond in proteins or peptides [1,2]. The inhibitors are designed to substitute the scissile bond present in substrates by a moiety which is resistant to the enzymatic hydrolysis [3]. The phosphorus atoms mimic the tetrahedral transition state of the substrate processing in the catalytic reaction.

Phosphinic dipeptide analogs are obtained in several synthetic pathways [4]. However, nucleophilic substitution of the Morita-Baylis-Hillman adducts with H-phosphinic compounds was rarely reported. The multistep procedure involved preparation of two starting materials: aminoalkyl-H-phosphinic acid in the reaction of hypophosphorus acid with selected aldehyde, and Morita-Baylis-Hillman adducts. Subsequently, the reaction of both building blocks gave target products, which were purified and characterized, then deprotected.

Phosphinodehydropeptides and phosphinodipeptides with non-canonical P1’ side-chain groups were suggested as improved ligands for selected metalloaminopeptidases. Their interactions with enzymes were analyzed computationally. The conformation of the compounds was optimized in the Discovery Studio with the use of the CHARMM force field. The active site of human aminopeptidase N was recreated by use of crystallographic data available in the PDB database [6]. Docking was performed in the Discovery Studio with LibDock algorithm [7]. The assessment criterion was correct interaction of the compounds with the zinc atom, which assigned ligands as transition state analogs.

The synthetic approach is presented and discussed. The inhibition constant were measured in kinetic studies for the chosen aminopeptidase. The score of molecular modeling of selected products bound in the active site of human aminopeptidase N is also given.

Key words: peptides, synthesis, Morita-Baylis-Hillman adducts, molecular modelling References: [1] A. Mucha, M. Drąg, J. P. Dalton, P. Kafarski, Biochimie 92 (2010) 1509-1529. [2] D. Georgiadis, V. Dive, Topics Curr. Chem. 360 (2014) 1-38. [3] A. Ilker, C. D. Hall, A. R. Katritzky, Chem. Soc. Rev. 43 (2014) 3575-3594 [4] A. Mucha, Molecules 17 (2012), 13530- 13568. [5] J. Grembecka, A. Mucha, T. Cierpicki, P. Kafarski, J. Med. Chem. 46 (2003) 2641-2655. [6] A. H. Wong, D. Zhou, J. M. Rini, J. Biol. Chem. 287 (2012) 36804-36813. [7] S. N. Rao, M. S. Head, A. Kulkarni, J.M. LaLonde, J. Chem. Inf. Model. 46 (2007) 2159-2171


2 0 1 7 March 20 - 22


O 1 6

SYNERGIC EFFECT OF MONOPHOS LIGANDS ON HYDROFORMYLATION Hubert Meissel, Sofia Papadouli, Paul Pringle


School of Chemistry, University of Bristol, Bristol, UK

The hydroformylation of olefins, catalysed by rhodium complexes is largest scale industrial application of homogeneous catalysis. [1] The aldehyde products are extensively used as precursors to solvents, plasticizers, pharmaceuticals and other fine chemicals. In the last five decades, many ligands have been developed to improve the regioselectivity towards the higher value linear aldehydes. The hydroformylation catalyst based on Rh-PPh3 complexes has found many applications. [2] Our focus has been on Rh catalysts based on pyrrolyl phosphines such as PPyr3 which have strongly π-accepting properties.[3] We have observed a synergic effect on the hydroformylation of 1-hexene using mixtures of PPyr3 and PPh3 ligands (see Figure 1).

In an attempt to harness this synergic effect, the synthesis of the unsymmetrical bidentate ligand 1 based on xanthene has been carried out. The hydroformylation catalysis results obtained with Rh/1 complexes will be presented.

References: [1] A. Behr, P. Neubert, Applied Homogeneous Catalysis, WILEY-VCH, Germany, 2011. [2] R. Franke, D. Selent, and A. Börner, Chem. Rev., 2012, 112, 5675−5732. [3] S. Papadouli, PhD Thesis, Bristol University, 2016. O. Diebolt, H. Tricas, Z. Freixa, and P. W. N. M. van Leeuwen, ACS Catal., 2013, 3, 128−137.

0

10

20

0/20 5/15 10/10 15/5 20/0

5 12

16 21

14 Selectivity l:b

Ratio of eq. PPyr3/PPh3

Figure 1: Rh-catalysed hydroformylation of 1-hexene with different ratios of PPyr3/PPh3, [Rh(acac)(CO)2] = 0.25 mol% in toluene (1.5 mL), CO/H2 =10/10 bars, 90 °C, [1-hexene]/[Rh] = 670, monocell autoclave. a l:b determined at 30-40% of

conversion by GC and NMR analysis, using internal standards decane and dodecane..

O

tButBu

PPh2 PPyr21


2 0 1 7 March 20-22


O 1 7

Multidentate 2-pyridyl-phosphine ligands – towards ligand tuning and chirality

Schirin Hanf1, Raúl García-Rodríguez1, Evamarie Hey-Hawkins2 and Dominic S. Wright1 e-mail: [email protected]

1Chemistry Department, University of Cambridge, Lensfield Road, CB2 1EW, Cambridge, UK 2Institute of Inorganic Chemistry, Faculty of Chemistry and Mineralogy, Leipzig University,

Johannisallee 29, 04103 Leipzig, Germany Asymmetric homogeneous catalysis provides access to complex, chiral substrates in a variety of key organic transformations. Although a range of phosphorus-based chiral ligands are used extensively in asymmetric catalysis, other main group metal- and non-metal-based ligand arrangements, like pyridyl-phosphines, have been largely overlooked in this field.[1]

Therefore, in the current work a range of multidentate pyridyl-phosphine ligands are synthesised, through the incorporation of a variety of alcohols into (amino)pyridyl-phosphine frameworks.[2] The stoichiometric reactions of (R2N)xP(2-py)3-x (2-py = 2-pyridyl) with alkyl as well as aryl alcohols yield (alkoxy)pyridyl-phosphines (RO)xP(2-py)3-x (R = Me, 2-Bu, Ph). This synthetic procedure not only allows to tune the electronic and steric character of the pyridyl-phosphines but also gives the opportunity to introduce enantiomerically pure alcohols, like (R)-(−)-2-BuOH and (S)-(+)-2-BuOH, and as such provides a very convenient two-step route to chiral multidentate pyridyl-phosphine ligand sets.

Coordination studies of the (amino)pyridyl-phosphines and (alkoxy)pyridyl-phosphines with copper(I) reveal that ligands with two N donor atoms form dimeric arrangements (Fig. 1, left), while (PhO)2P(2-py), incorporating only one N donor atom, shows completely different coordination behaviour (Fig. 1, right).

Figure 1: Dimeric structure of [(MeCN)Cu{(Et2N)2P(2-py)}]2(PF6)2 (left) and structure of

[(MeCN)Cu2{(PhO)2P(2-py)}3](PF6)2·3THF (right).

Key words: pyridyl-phosphines, catalysis, chirality References: [1] I. Ojima, Asymmetric Synthesis, Wiley-VCH, 3rd edn, 2008.

[2] S. Hanf, R. García-Rodríguez, S. Feldmann, A. D. Bond, E. Hey-Hawkins, D. S. Wright, Dalton Trans., DOI: 10.1039/c6dt04390a.


2 0 1 7 March 20-22


O 1 8

SYNTHESIS OF FLUORINATED PHOSPHONIC ANALOGUES OF PHENYLGLYCINE

Weronika Wanat1, Paweł Kafarski1

e-mail: [email protected] 1 Institute of Organic Chemistry, Biochemistry and Biotechnology, Wroclaw University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland

Aminophosphonic acid derivatives constitute interesting class of compounds with a broad spectrum of biological activity. Due to their pharmacological properties they play an important role in bioorganic and medicinal chemistry. These compounds possess ability to inhibit different class of enzymes1-2. Among them aminophosphonate derivatives bearing phenyl ring have been synthesized and evaluated as inhibitors of certain enzymes with analogues of phenylglycine being lead compounds for phenylalanine ammonia lyase (PAL) effectors.

Aminophosphonates containing fluorine and other substituents (eg. Cl, CH3, CN) in the aromatic ring have been synthesized by Oleksyszyn-Soroka reaction3-5. The structures of these compounds was determined by means of 1H NMR, 13C NMR, 19F NMR, 31P NMR and ESI-MS methods.

O

F, Cl, CH3

NH2

PO3H2

1. AcNH2/AcCl2. PCl33. Hydrolysis

F, Cl, CH3

Fig. 1 Preparation of α-aminophosphonic acid analogues of phenylglycine

Key words: α-aminophosphonic acids, phenylglycine, PAL References: [1] P. Kafarski, B. Lejczak, Curr. Med. Chem. – Anti-Cancer Agents, 2001, 1, 301-312. [2] A. Mucha, P. Kafarski, Ł. Berlicki, J. Med. Chem. 2011, 54, 5955-5980. [3] J. Oleksyszyn, M. Soroka, and J. Rachon, Chimia, 1978, 32, 253. [4] J. Oleksyszyn, R. Tyka, and P. Mastalerz, Synthesis, 1978, 479. [5] J. Oleksyszyn, E. Gruszecka, P. Kafarski, and P. Mastalerz, Monatsh. Chem., 1982, 22, 59.


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O 1 9

DIRECT CATALYTIC SYNTHESIS OF SODIUM DIARYLPHOSPHINATES AND THEIR CORRESPONDING ACIDS FROM SODIUM PHOSPHINATE

Laurian BOTEZ,1, 2 G. Bas de JONG,1 Berth-Jan DEELMAN2 and J. Chris SLOOTWEG,1 [email protected]; [email protected]; [email protected]

1 Van 't Hoff Institute For Molecular Sciences, Universiteit van Amsterdam, PO Box 94157, 1090GD Amsterdam, the Netherlands

2 ARKEMA B.V., location Vlissingen, P.O. Box 70, 4380AB Vlissingen, the Netherlands

Organophosphinic acids R2P(O)OH and their derivatives are relevant compounds as flame retardants, in solar cells, as ligands for catalysis, in pharmaceutical applications and in metal extraction. We have developed a novel synthesis based on the direct use of the industrially produced sodium phosphinate monohydrate 1 towards diarylphosphinate salts 2 and their corresponding acids 3. This versatile method tolerates functional groups, such as carbonyls, that are incompatible with classical Grignard or organolithium reagents and avoids the need for PCl3, or alkyl- and ammoniumphosphinates (scheme 1).[1]

ArBr+

41 - 86 % yield

H2OP

O

O-Na+H

HPO

OHArAr

[Pd] P^Pbase, solvent

Ar = -C6H5, -C6H4Me-4,

-C6H3Me2-3,5, -C6H4C6H5-4, -C6H4OMe-4, -C6H4OMe-3,

-C6H4F-4, -C6H4COMe-4,

-C6H4COOH-4, -C6H4NO2-4

H+

PO

O-Na+Ar

Ar

1 2 3

Scheme 1. Synthesis of sodium diarylphosphinates 2 and diarylphosphinic acids 3 from NaH2PO2⋅H2O.

We extended this methodology towards highly electron deficient perfluorinated diarylphosphinic acids (scheme 2) and are currently targeting the synthesis of highly Lewis acidic arylphosphinate complexes for application in organic synthesis as well as coordination chemistry and catalysis.

POHO

POHO

F F

F3C

CF3 CF3

CF3F

F

F

F

F

F

coordinationand

catalysis

Scheme 2. Extension to highly electron deficient diarylphosphinic acids and towards coordination and catalysis.

We gratefully acknowledge funding by the EU - Marie Curie ITN SusPhos, GA No. 317404. Keywords: Phosphinate · Homogeneous catalysis · Cross coupling · Palladium References: [1] L. Botez, G. B. de Jong, J. C. Slootweg, B.-J. Deelman, doi:10.1002/ejoc.201601222


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O 2 0

DiPhos-Pt(0) Monocarbonyl Complexes for Small Molecule Activation

Krishna Mistry1, Duncan F. Wass1 and Paul G. Pringle1. [email protected]

1 School of Chemistry, University of Bristol, Cantock’s Close, Bristol, BS8 1TS, UK.

Small molecules, such as H2, CO and CO2, have the potential to be sustainable building blocks in the chemical industry. However, developing new catalytic transformations of these molecules into useful compounds can be challenging. In recent years, the activation of small molecules by Frustrated Lewis Pairs (FLPs) has grown exponentially.[1] Initially, typical FLP chemistry involved Main Group Lewis acid-base pairs acting cooperatively to activate small molecules such as H2 and this led to successful applications in hydrogenation catalysis.[2] We, amongst others,[1,3] have extended this chemistry to involve early transition metal-containing FLPs which are capable to undergoing novel transformations such as cleavage of carbon-halogen bonds.[4] However, exploiting these reactions for catalysis has been inhibited due to the high oxophilicity of the early transition metals. We have recently reported the use of an electron rich platinum(0) complex where the metal centre acts as the Lewis base cooperatively with tris(pentaflurorophenyl)borane (BCF) as the Lewis acid.[5] The results presented here will include FLP activity and the unprecedented coupling of CO and ethene to form an acyl borate.[6] It will also be shown how changing the electronic properties of the system by altering the diphosphine ligand backbone has a significant effect on the activation of dihydrogen. Further investigations are in progress for the potential application of this system for catalytic activation of small molecules.

Key words: FLP, activation, platinum. References: [1] D. W. Stephan, G. Erker, Angew. Chem. Int. Ed. 49 (2010) 46-76, Angew. Chem. Int. Ed. 54 (2015) 6400-6441. [2] D. W. Stephan, Org. Biomol. Chem. 10 (2012) 5740-5746. [3] S. R. Flynn, D. F. Wass, ACS Catal. 3 (2013) 2574-2581. [4] A. M. Chapman, M. F. Haddow, D. F. Wass, J. Am . Chem. Soc. 133 (2011) 18463-18478 [5] S. J. K. Forrest, P. G. Pringle, H. A. Sparkes, D. F. Wass, Dalton Trans. 43 (2014) 16335-44. [6] S. J. K Forrest, J. Clifton, N. Fey, P. G. Pringle, H. A. Sparkes, D. F. Wass, Angew. Chem. Int. Ed. 54 (2015) 2223-2227.

X

X

tBu2P

PtBu2

Pt CO

tBu2P

PtBu2

Pt

H

CO

HB(C6F5)3

tBu2P

PtBu2

PtO B(C6F5)3

H2X = CH2

C2H4X = CH2

H2X= O

O

O

tBu2P

PtBu2

Pt

H

CO

O

O

tBu2P

PtBu2

Pt

O

O

tBu2P

PtBu2

Pt

H

H

O

O

tBu2P

PtBu2

PtH

O

O

tBu2P

PtBu2

Pt

H

CO


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O 2 1

β-HYDROXYALKYLPHOSPHINE SULFIDES- AN INTRIGUING REACTIVITY

Katarzyna Włodarczyk1, Marek Stankevič1

e-mail: [email protected] 1Department of Organic Chemistry, Faculty of Chemistry, Marie Curie-Skłodowska University,

Gliniana 33, 20-614 Lublin, Poland

Stereoselective deprotonation using a chiral base is a well-known method of the synthesis of P-stereogenic compounds.[1] Desymmetrization of symmetrically substituted tertiary phosphine derivatives using a chiral base was used for the synthesis of P-chiral organophosphorus compounds, mainly diphosphine ligands. During the course of our current research project we were interested in the synthesis of P-chiral cyclic organophosphorus compounds possessing phosphaindane skeleton using intramolecular cationic cyclization reaction.[2] With strong inorganic acids the cyclization proceeds smoothly but with less strong acids or in the presence of Lewis acid the main products were the corresponding β-thioloalkylphosphine oxides.

PS

R'OH

AlCl3 (5

.0) PO

H2SO4

R

CH3COOH

PO SH

89%

R=R'= Et

H3PO4

R=R'= MeP

O 74%

SH59%

Herein, we wish to present some results concerning the attempted synthesis of

P-stereogenic cyclic phosphine derivatives in a non-racemic form and novel as well unexpected method of the synthesis of β-thioloalkylphosphine oxides through the intramolecular phosphorus-to-carbon sulfur atom migration. Key words: Cyclization, Desymmetrization, β-hydroxyalkylphosphine sulfides, Intramolecular, β-thioloalkylphosphine oxides

References: [1] (a) D. Hoppe, F. Hintze, P. Tebben, M. Paetow, H. Ahrens, J. Schwerdtfeger, P. Sommerfeld, J. Haller, W. Guarnieri, S. Kolczewski, T. Hense and I. Hoppe, Pure Appl. Chem., 66(1994) 1479-1486, (b) A. R. Muci, K. R. Campos and D. A. Evans, J. Am. Chem. Soc., 117 (1995) 9075-9076. [2] A. S. Bogachenkov, A. V. Dogadina, V. P. Boyarskiy, A. V. Vasilyev, Org. Biomol. Chem., 13 (2015) 1333-1338 This work has been supported by National Science Center (research project 2012/07/E/ST5/00544)


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O 2 2

Functionalization and Transfer of Polypnictogen Units

Andreas E. Seitz1 and Manfred Scheer1 e-mail: [email protected]

1 Institute of Inorganic Chemistry, University of Regensburg, Universitätsstr. 31, 93040 Regensburg, Germany

Since the beginning of the 1970s, the activation of white phosphorus has become a rapidly growing field in Inorganic Chemistry.[1-4] In the past years, the concept of transfer reactions came into focus to synthesize Pn and Asn containing compounds by transferring the En units (E = P, As) between different fragments under mild reaction conditions. Thereby, we showed that the phosphorus and arsenic compounds [Cp''2Zr(η1:1-E4)] (Cp'' = 1,3-C5H3tBu2; E = P, As) are promising pnictogen transfer reagents. Recently, we succeeded for example in the preparation and characterization of the pnictogen-silicon analogues of benzene (see scheme below).[5] An insight into these results will be given demonstrating the potential of transfer reactions for the synthesis of En (E = P, As) containing transition metal complexes and main group compounds.

Key words: phosphorus, arsenic, transfer reactions, NMR spectroscopy, DFT studies References: [1] B. M. Cossairt, N. A. Piro, C. C. Cummins, Chem. Rev., 110 (2010) 4164 - 4177.

[2] M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini, Chem. Rev., 110 (2010) 4178 - 4235.

[3] M. Scheer, G. Balázs, A. Seitz, Chem. Rev., 110 (2010) 4236 - 4256.

[4] N. A. Griffin, J. D. Masuda, Coord. Chem. Rev., 255 (2011) 1342 - 1359.

[5] A. E. Seitz, M. Eckhardt, A. Erlebach, E. V. Peresypkina, M. Sierka, M. Scheer, J. Am. Chem. Soc. 138 (2016) 10433-10436.


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“ B a b e ș - B o l y a i ” U n i v e r s i t y , F a c u l t y o f C h e m i s t r y a n d C h e m i c a l E n g i n e e r i n g , C l u j - N a p o c a , R O M A N I A O23

INFLUENCE OF THE PHOSPHOROUS IN THE ELECTRONIC

STRUCTURE OF COPPER AND NICKEL SALEN-TYPE COMPLEXES

Irene Mustieles Marín, Thibault Cheisson, Marie Cordier, Gregory Nocton, Carine

Clavaguera, Duncan Carmichael, Audrey Auffrant.

[email protected]

Laboratoire de Chimie Moléculaire (Ecole Polytechnique)

Phosphasalen ligands developed in our laboratory can be considered as the phosphorous

analogues of salen ligands where the imine functions have been substituted by

iminophosphorane functions.1 The presence of the P-N bond makes these ligands more

electron-donating and more flexible than salen analogues. They are able to stabilize high-

valent metal complexes, as in the case of a Ni phosphasalen complex which was characterized

as a NiIII

complex in solution and in solid state. This oxidation state has not been obtained

before with salen-type ligands.2

In order to determine the influence of the different substituents in the electronic structure of

these complexes, different ligands have been synthesized by changing the bridge motif, the

phenolate substituents and the phosphorus substituents. The corresponding Cu and Ni

complexes have been synthesized and we have studied the one-electron oxidation products.

Because these ligands show redox non-innocent behavior, the ambiguous situation

encountered upon oxidation makes necessary the use of numerous methods to determine the

oxidation state of the metal in the complex. Besides UV-vis, NMR, cyclic voltammetry and

X-ray diffraction, SQUID and EPR techniques were crucial for the electronic structure

determination.

Key words: salen-type ligands, redox non-innocent, one-electron oxidation

[1] T. P. A. Cao, S. Labouille, A. Auffrant, Y. Jean, X. F. Le Goff, P. Le Floch Dalton Trans. 40

(2011) 10029-10037.

[2] T. P. A. Cao, G. Nocton, L. Richard, X. F. Le Goff, A. Auffrant Angew. Chem. Int. 53 (2014)

1368-1372.


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O 24

In situ Spectroelectrochemistry and Preparative Electrosynthesis of Phosphorus-based Bipyridinium Derivatives

Stephen Schulz, David Harting, Felix Hennersdorf and Jan J. Weigand*


TU Dresden, Department of Chemistry and Food Chemistry, 01062 Dresden, Germany Spectroelectrochemical methods (SEC) are powerful tools for the in situ characterization of electrochemically generated reactive species like phosphorus-centered radicals.[1] In our investigation towards stable and reversible redox active phosphorus compounds we synthesized the bipyridinium derivatives 1[OTf] and 2[OTf]2 by onio-substitution.[2] This contribution is focused on the preparative electrosynthesis of the stable and strongly colored reduction products of cation 1+ (1• & 1-) and of dication 22+ (2+• & 2). In situ UV-VIS-NIR spectroelectrochemical cyclic voltammetry of dication 22+ is used to elucidate its two-stage (deep blue and deep red) electrochromic behavior.[3]

Sub sequential preparative electrochemical reduction of cation 1+ to the stable radical 1• and anion 1- leads to the reversible formation unusual dimer (1)2. The mechanism was investigated be the use of in situ CV and ex situ EPR spectroscopy during the electrolysis. In situ UV-VIS-NIR spectroelectrochemistry of dication 22+ in a novel thin-layer flow cell design reveals the possibility of reversible switching between the deep colored intermediates 22+ 2+• 2 with high cycle stability.[3] This represents the first step of introducing reversible redox active biyridinium moieties into phosphane oxide building blocks. Key words: spectroelectrochemistry, electrosynthesis, radicals, bipyridinium, electrochromism

References: [1] K. Schwedtmann, S. Schulz, F. Hennersdorf, T. Strassner, E. Dmitrieva, J. J. Weigand, Angew. Chem. Int. Ed. 54 (2015) 11054–11058. [2] R. Weiss, B. Pomrehn, F. Hampel, W. Bauer, Angew. Chem. Int. Ed. 34 (1995) 1319–1321. [3] a) P. R. Somani and S. Radhakrishnan, Mater. Chem. Phys. 77 (2003) 117–133; b) R. J. Mortimer, Electrochim. Acta 44 (1999) 2971–2981. Acknowledgement: We thank the European Research Council (ERC starting grand, SynPhos 307616) for financial support.


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O 2 5

REACTIVITY OF DONOR-SUBSTITUTED PHOSPHININES - FROM COORDINATION POLYMERS TO λ5-PHOSPHININES

Steven Giese, Christian Müller e-mail: [email protected], [email protected]

Freie Universität Berlin, Institute of Chemistry and Biochemistry, Fabeckstraße 34/36, 14195 Berlin Due to their unique electronic properties, λ3σ2-phosphinines bind preferentially to late transition metal centers in low oxidation states. With the incorporation of additional donor atoms in the ligand framework, a broad spectrum of interesting coordination compounds became accessible and a variety of complexes with unusual features and exciting new properties have been presented in recent years.[1,2] In this respect, the reaction of 4-(4-(methylthio)-phenyl)-2,6-di-m-tolylphosphinine with CuCl and CuBr resulted in the formation of hitherto unknown coordination polymers with phosphinines as bridging ligands.

By increasing the number of thiomethyl substituents in the ligand framework, new cross-linked structures could, in principle, be formed.[3] For this reason, the synthesis of 2,4,6-tris(4-(methylthio)phenyl)phosphinine 1 and its coordination chemistry with different coinage metals was investigated. Surprisingly, the reaction with AuCl∙SMe2 led to the formation of an unprecedented 1,1-dichloro-λ5-phosphinine. We attribute those results to the unusual electronic properties of 1, which are currently under investigation.

These first results on the coordination chemistry of thiomethyl substituted phosphinines open a new chapter in the versatile coordination chemistry of these ligands. Key words: phosphinines, coordination chemistry, inorganic polymer References: [1] G. Märkl Angew. Chem. 78 (1966) 907. [2] a) C. Müller, J. A. W. Sklorz, I. de Krom, A. Loibl, M. Habicht, M. Bruce, G. Pfeifer, J. Wiecko Chem. Lett. 43 (2014) 1390-1404; b) C. Müller, L. E. E. Broeckx, I. de Krom, J. J. M. Weemers Eur. J. Inorg. Chem. 2 (2013) 187-202; d) A. Loibl, I. de Krom, E. A. Pidko, M. Weber, J. Wiecko, C. Müller Chem. Commun. 50 (2014) 8842; e) C. Müller, D. Wasserberg, J. Weemers, E. A. Pidko, S. Hoffmann, M. Lutz, A. Spek, S. Meskers, R. Janssen, R. van Santen, D. Vogt Chem. Eur. J. 13 (2007) 4548-4559. [3] G. Huang, Y.-Q. Sun, Z. Xu, M. Zeller, A. D. Hunter, Dalton Trans. 26 (2009), 5083-5093.


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O 2 6

When carbenes meet phosphorus – a computational study

Dániel BUZSÁKI, Zsolt KELEMEN, László NYULÁSZI e-mail: [email protected]

Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Szt Gellért tér 4, H-1111 Budapest, Hungary

The bonding in phosphorus ylides A (alternatively described with a formal double

bond) can be understood as a phosphane carbene adduct [1]. In recent reactions between stable carbenes and phosphanes, however, various including dative single bonded compounds B and phosphanes C were obtained [2]. The aim of our work is the investigation of the relative stability of these systems depending on the carbenes (1-8) and the substituents at phosphorus by using DFT calculations. Also we investigate the bonding in these compounds by Bader analysis and NRT studies.

We have established that with the parent carbene the ylidic/double bonded form A can indeed be obtained, with stabilized carbenes a weak dative bonded adduct B can be formed, and rearrangement to phosphanes can happen. For some cases both A and B structures exist giving rise for the rare bond-stretch isomerism [3].

Me2N

Me2N

N

N

Me

Me

N

N

Me

Me

N

N

Me

Me

NMe

carbene PX3carbene

PX2

X

H2C: Cl2C:carbene:

1 2 3 4 5 6 7

X: H, F, Cl, NMe2

A B

carbene PX3

C

FeN

N

Me

Me

8

carbene PX3

Key words: DFT calculations, carbene adducts, bond-stretch isomerism

References: [1] G. Trinquier, J.-P. Malrieu J. Am. Chem. Soc 109 (1987) 5303-5315 [2] (a) G. D. Frey, J. D. Masuda, B. Donnadieu, G. Bertrand, Angew. Chem. Int. Ed. 49 (2010), 9444–9447. (b) M. Bispinghoff, A. M. Tondreau, H. Grützmacher, C. A. Faradji, P. G. Pringle, Dalton Trans. 45 (2016), 5999-6003 [3] (a) J. Chatt, L. Manojlovic-Muir, K. W. Muir, J. Chem. Soc., Chem. Commun. 1971, 655-656. (b) L. Nyulászi, T. Veszprémi, B. A. D’Sa, J. G. Verkade, Inorg. Chem. 35 (1996), 6102-6107; (c) T. Kárpáti, T. Veszprémi, N. Thirupathi, X. Liu, Z. Wang, A. Ellern, L. Nyulászi, J. G. Verkade, J. Am. Chem. Soc. 128 (2006), 1500-1512


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O 2 7

BISMESITOYLPHOSPHINIC ACID – A POTENT REAGENT FOR THE PHOTOCHEMICAL PREPARATION OF CU NANOPARTICLES IN HYDROGELS

Andreas Beil, 1 Georgina Müller, 1 Frank Krumeich, 1 Bodo Hattendorf, 1

Zhongshu Li, 1 Amos Rosenthal, 1 Hansjörg Grützmacher*1 E-Mail: [email protected], [email protected]

1ETH Zürich, D-CHAB, Laboratory of Inorganic Chemistry, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland

P

O

O

Mes

Mes

OO

P

O

OMes

Mes

OO

Cu

OH2

OH2

We present the photochemical reduction of aqueous copper(II) sulfate in the presence of the readily available photoinitiator bismesitoylphosphinic acid (BAPO-OH) [1,2] to obtain metallic copper nanoparticles. The coordination behavior of BAPO-OH toward Cu(II) was investigated by single crystal X-ray analysis. The described method allows to access colloidal metallic copper and nanoscopic Cu particles of different size and morphology. This was shown by dynamic light scattering (DLS), scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM). Energy dispersive X-ray (EDX) analysis and X-ray powder diffraction confirmed the purity of the obtained Cu samples. Finally, we could show that hydrogels containing nanoscopic copper can be prepared by using the Cu(II) complex of BAPO-OH as both photoinitiator and Cu-source [3].

Key words: Bismesitoylphosphinic acid, BAPO photoinitiator, copper nanoparticles, hydrogels

References: [1] WO2014095724A1 (2014). [2] G. Müller et al., Macromol. Rapid Commun. 36 (2015) 553-557. [3] A. Beil et al., manuscript in preparation.


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O 28

SYNTHESIS OF PHOSPHORUS CONTAINING FLAME RETARDANTS AND INVESTIGATION FLAME RETARDANT BEHAVIOUR ON THE

TEXTILE APPLICATIONS

Muhammed Kanat1, Tarik Eren2

[email protected]

Department of Chemistry, Yildiz Technical University, Istanbul, Turkey

Cotton fabrics have been one of the most widely used bio-based textiles all over the world. They have been widely applied in both civilian and military fields due to their excellent properties, such as hydrophilicity, air permeability, softness and comfortableness and so on. However, the flammability showed their weakness and badly limited the production of high performance flame retardant textile products [1]. Many people constantly use halogen-free phosphorus compounds as flame retardants for cotton textiles. They are cheap to manufacture, are less volatile and toxic, have good thermal stability and promote char formation during the burning process. Some studies [2,3] have shown that, phosphorus-compounds can catalyze char formation and reduce the flammability of cotton textiles. In this study, we have synthesized reactive phosphorus containing flame retardants that can be covalently attached to the textile surface. Thermal properties of the textile was investigated by TGA, UL94 and microcalorimetric studies.

Key words: Flame retardancy, phosphorus, textile application

References: [1] Y.Y. Liu, X.W.Wang, K.H. Qi, J.H. Xin, J. Mater. Chem. 18, 2008 3454–3460. [2] W.E. Franklin, S.P. Rowland, J. Appl. Polym. Sci. 24, 1979 1281–1294. [3] H. Yang, C.Q. Yang, Q.L. He, Polym. Degrad. Stab. 94, 2009 1023–1034.

Acknowledgements

This study was supported by COST action CM1302 (SIPs) TUBITAK 114Z666 and the authors gratefully acknowledge the COST action CM1302 (SIPs) TUBITAK 114Z666.


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POSTER PRESENTATIONS


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P 1

SYNTHESIS AND CARACTERIZATION OF CYCLIC PHOSPHORUS-BASED POLYBUTENE BY USING ROMP PATHWAY

Ilay Ceren Acar1, Tarik Eren1*

[email protected]

Chemistry, Yildiz Technical University, Istanbul, Turkey

Phosphorus-containing high performance polymers have aboundant interest, mainly

due to good mechanical features and their excellent fire resistance. These mechanical features are adhesive to metals, bone and dentin. On the other hand they have biocompatibility, hemocompatibility, and protein adsorption resistence. Due to these all features, they are used in broad application areas. One of them is biomedical field. It mainly describes relevant works achieved on these materials for various applications: dentistry, regenerative medicine, and drug delivery. [1] Another one is their application of flame retardant properties. Today, brominated aromatic flame retardants used in a wide range of products, incluiding textiles, electronics due to enviromental concerns and releasing hydrogen halide gas upon combustion are restricting their use, and requires the development of new flame retardants. The new one can be phosphorous-containing polymer. [2]

In this study, the benefits of ring opening metathesis polymerization, in order to build well-defined copolymers with narrow distrubition of molecular weights,and phosphorus chemistry is applied for a highly versatile system. First, 1,5 Cyclooctadiene was converted to mono-epoxy cyclooctene with epoxidation reaction by using m-chloroperbenzoic acid. After that, it was converted to 5-cyclooctene-1,2-Diol by using sulfuric acide catalyst. Then ıt was reacted with diethyl chlorophosphate. Finally cyclic-phosphorous containing monomer was converted to polybutene using Grubbs catalyst. (Scheme1) Structures of the polymers were confirmed by FTIR, 1H NMR, 13C NMR 31P NMR, spectroscopies. The thermal properties of the polymers were also investigated.

Scheme 1. Synthesis of cyclic phosphorus containing polybutene

Key words: ROMP, cyclic phosphorus, polycyclooctene

References [1] M. Filippo, W. Manfred, L. Katharina, W.R. Frederik, Macromolecules, 2012, 45, 8511-8518. [2] P. Doris, K. Andreas, K. Hartnut, J. Dşeter, H. Liane, S. Holger, L. Micheal, J. Klaus, V. Brigitte, Macromolecular Journals, 2015 , 216 , 1447-1461. Acknowledgements

This study was supported by COST action CM1302 (SIPs) TÜBİTAK 114Z666 and the authors gratefully acknowledge the COST action CM1302 (SIPs) TÜBİTAK 114Z666


2 0 1 7 March 20-22

“ B a b e ș - B o l y a i ” U n i v e r s i t y , F a c u l t y o f C h e m i s t r y a n d C h e m i c a l E n g i n e e r i n g , C l u j - N a p o c a , R O M A N I A P2

Synthesis of “onion-peel” dendrimers incorporating up to seven different types of

phosphorus groups in their structure

Anne-Marie Caminade1, Nadia Katir,

1,2 Nabil El Brahmi,

1,2 Jean-Pierre Majoral

1


1 Laboratoire de Chimie de Coordination (LCC-CNRS), 205 Route de Narbonne, BP 44099, Toulouse

Cedex 4, France 2 Euromed Research Institute, Engineering Division, Euro-Mediterranean University of Fes, Fès-

Shore, Route de Sidi Hrazem, 30070 Fès, Morocco.

Dendrimers are hyperbranched macromolecules, constituted of repetitive building

units, elaborated step-by-step in an iterative process. The main properties of dendrimers are

generally due to their numerous terminal functions, which can be easily modified at will, to

afford properties in diverse fields ranging from catalysis to materials and biomedical uses [1].

We are specialized since a long time in the synthesis

of phosphorus-containing dendrimers having a uniform

internal structure [2]. The modularity of our method of

synthesis is very high, and affords the possibility to

incorporate different functions at each layer (each

generation). We have recently proposed the synthesis of an

“onion-peel” dendritic structure, composed of different

layers with sequential functional diversity. The largest

compound of this family incorporates in its structure seven

different types of phosphorus derivatives, as shown in the

illustration [3].

This compound is in particular characterized by 31

P

NMR, which displays seven families of signals,

corresponding to the cyclotriphosphazene core, the

aminothiophosphate groups of the first and second

generations, the P=N-P=S-Au groups of the third generation

(two doublets), the PF6- counter ions of viologen units, and the phosphonate terminal

functions.

Key words: Dendrimers; macromolecules; onion-peel structure; functional diversity; 31

P

NMR

References: [1] A.M. Caminade, C.O. Turrin, R. Laurent, A. Ouali, B. Delavaux-Nicot (Eds.), Dendrimers.

Towards Catalytic, Material and Biomedical Uses, John Wiley & Sons, Chichester (UK), 1–

538, 2011.

[2] N. Launay, A.M. Caminade, R. Lahana, J.P. Majoral, Angew. Chem. Int. Ed. Engl. 33

(1994) 1589–1592.

[3] N. Katir, N. El Brahmi, A. El Kadib, S. Mignani, A.M. Caminade, M. Bousmina, J.P.

Majoral, Chem. Eur. J. 21 (2015) 6400–6408 (hot paper).


2 0 1 7 March 20-22


Small Molecule and Polymer Derivatives of Group 15 Heterofulvenoids

Daniel Morales Salazar, Muhammad Anwar Shameem, Jens Uhlig and Andreas Orthaber*

[email protected]

*Department of Chemistry, Ångström Laboratories, Molecular Inorganic Chemistry,

Uppsala University, Box 523, 75120 Uppsala, Sweden

Fulvenoid type molecules as building blocks for conjugated systems possess a unique

electronic structure and allow interesting applications. Our main goal is to introduce Group 15

elements (phosphorus and arsenic) into π-conjugated frameworks, where the heteroelement

plays a crucial role for the function of the resulting materials. We will explore how

unsaturated main group moieties – arsa- and phosphaalkenes, which are known to stabilize the

lowest unoccupied molecular orbitals, effect the electronic structure of the whole conjugated

system.1 Moreover we are interested in the post-functionalization at the heteroelement and

how that impacts the opto-

electronic properties.2

We have studied two rigid

molecular building blocks,

which are based on a hetero-

fulvenoid core with

annulated benzene (= “fluorene”) or thiophene (“cyclopentadithiophene”) units. In our

studies, the heteroatom is incorporated as an exocyclic C=E double bond directly into the π-

conjugated framework. We have explored these building blocks as monomers for the

synthesis of polymeric materials incorporating unsaturated E=C units as part of their

conjugated backbone,3 as well as (donor-substituted) small molecules for light activated

processes, e.g. light harvesting and excited state

charge transport.4

Key words: phosphaalkene,

arsaalkene, polymer, time-resolved spectroscopy

Acknowledgment: The authors thank the Swedish research council, Carl-Trygger foundation, COST action SIPs (Smart Inorganic Polymers) and the Olle-Engkvist foundation for financial support. References: [1] M. A. Shameem and A. Orthaber, Chem. Eur. J. 22 (2016) 10718–10735.

[2]. C. Reus, T. Baumgartner, Dalton Trans. 2016, 45, 1850-1855

[3] D. Morales Salazar, E. Mijangos, S. Pullen, M. Gao, A. Orthaber, Chem. Commun. 2017, 53, 1120

[4] A. El Nahas, M. A. Shameem, P. Chabera, J. Uhlig, A. Orthaber, manuscript under review


2 0 1 7 March 20-22


THEORETICAL STUDY ON A SET-INDUCED POLYMERIZATION OF

OXAPHOSPHIRANES

Arturo ESPINOSA FERAO1, Rainer STREUBEL

2


1 Departamento de Química Orgánica, Facultad de Química, Universidad de Murcia, Campus de

Espinardo, 30071 Murcia (Spain) 2 Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität Bonn.

Gerhardt-Domagk-Strasse 1, 53121 Bonn (Germany)

Oxaphosphiranes can be regarded as phospha-analogues of epoxides and, hence, a

related chemistry might be expected with respect to polymerizations. The ring strain in oxa-

phosphiranes[1]

is just slightly smaller than in epoxides, but still higher than in phos-

phiranes,[2]

for which two examples of polymerization have been reported.[3]

Moreover, we

recently recognized that oxidative single electron transfer (SET) of oxaphosphirane κP-

Cr(CO)5 complexes weakens the endocyclic P-C bond allowing easy ring cleavage to afford

an open-chain radical cation.[4]

Herein, results will be discussed concerning the computational

exploration of the initiation and the first propagation step in an oxidative SET-induced

polymerization of unligated oxaphosphiranes (1).

Key words: Oxaphosphiranes; polymerization; SET; DFT calculations References:

[1] O. Krahe, F. Neese, R. Streubel, Chem. Eur. J., 15 (2009) 2594-2601.

[2] A. Espinosa, R. Streubel, Chem. Eur. J., 17 (2011) 3166-3178.

[3] a) S. Kobayashi, J.-I.Kadokawa, Macromol. Rapid Commun. 15 (1994) 567-571;

b) L. A. Vanderark, T. J. Clark, E. Rivard, I. Manners, Chem. Commun (2006), 3332-

3333.

[4] A. Espinosa, R. Streubel, Chem. Eur. J., 18 (2012) 13405-13411.



2 0 1 7 March 20-22


ELECTROCHEMICAL PROPERTIES OF Pt(II) METAL COMPLEX OF

2,2’-BIPYRIDYL and BIS(DIPHENLYPHOSPHINEMETHYL)

AMINOBUTYL LIGANDS

Gülfeza KARDAS1 ,

Gurbet YERLIKAYA

1

e-mail:[email protected]

1Çukurova University, Faculty of Science, Department of Chemistry, 01330, Adana, Turkey

Metal pyridyl complexes are studied extensively in recent years due to their wide application

areas such as optical devices in production of new materials[1]. In this study, heteroleptic

Pt(II) metal complex of 2,2’-Bipridyl and bis(diphenylphosphinemethyl)amino ligands has

been synthesized using Schlenk method under nitrogen atmosphere at room temperature[2-3].

The structure of metal complex has been characterized by FT-IR, NMR (1H,

31P)

spectroscopic techniques. Electrochemical behavior of complexes has been investigated by

cyclic voltammetry. The oxidation and reduction potentials of platinum complex was

determined with three electrodes configuration at 25°C in 1x10-3

M metal complexes at glassy

carbon electrode in 0.1 M dichloromethane with solution TBAP as a supporting electrolyte.

HOMO and LUMO energies of the compound were calculated from the peaks onset

potentials.

a) b)

E (V) (Ag/AgCl)

-0.2 0.0 0.2 0.4 0.6 0.8 1.0

i (m

A)

-3e-5

-2e-5

-1e-5

0

1e-5

2e-5

Figure 1.a)Molecular Structure of Pt(II) metal complex of 2,2’-Bipyridyl and

bis(diphenylphosphinemethyl)amino ligands. b) Cyclic voltammetry behavior of 1x10-3

M Pt(II) metal

complex of 2,2’-Bipyridyl and bis(diphenylphosphinemethyl)amino ligands at glassy carbon electrode

in 0.1 M dichloromethane with solution TBAP as a supporting electrolyte at 100 mV/s scan rate.

Key words: Cyclic Voltammetry, Synthesis, Pt(II) complex

References: [1]Yam, V.W.W.,Lo, K. K.W., Chemical Society Reviews 1999. 28323-334.

[2]Keles, M., Keles, T.,Serindag, O., Transition Metal Chemistry 2008. 33, 6717-720.

[3]Favarin, L.R.V., Rosa, P.P., Pizzuti, L., Machulek, A.Jr., Caires, A.R.L., Bezerra, L.S., Pinto,

L.M.C., Maia,G., Gatto, C.C., Davi, F. B., Anjos, A.D., Antônio, G.C.L.R.V. Favarin et

al./Polyhedron 121 (2017) 185–190 Acknowledgement: The authors are greatly thankful to Unit of The Scientific Research Project Of Çukurova

University (BAP) for financial support (Project Number: FDK-2014-3517)

https://www.google.com.tr/url?sa=t&rct=j&q=&esrc=s&source=web&cd=1&cad=rja&uact=8&ved=0CBsQFjAA&url=http%3A%2F%2Fpubs.rsc.org%2Fen%2FJournals%2FJournal%2FCS&ei=rc-PVbyvHcm2swGQh6XACw&usg=AFQjCNHx5VeyG5BGvB7CpW-HORaMW_Jsnw&sig2=Nkf255cXzE_MiC4ZiwB8kw&bvm=bv.96783405,d.bGg

European Workshop on Phosphorus Chemistry - EWPC 14/2017 2 0 1 7

March 20-22

“Bab e ș - B o l ya i ” U n i ve r s i t y , F a c u l t y o f C h e mi s t r y a n d C h e mi c a l E n g i n e e r i n g , C l u j - N a p o c a , R O M A N I A P6

SYNTHESES AND REACTIVITY OF A GEMINAL AL/P BASED FRUSTRATED LEWIS PAIR BEARING RELATIVELY SMALL

SUBSTITUENTS

Damian PLESCHKA, Jana BACKS and Werner UHL

Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Germany

[email protected]

Hydroalumination of the alkynylphosphine 1 with dialkylaluminium hydrides afforded geminal Al/P based frustrated LEWIS pairs (FLPs) 2 in selective reactions. As previously shown FLP 2a (R = CMe3) is highly reactive towards a large number of different substrates, such as CO2

[1] or terminal alkynes[1]. This poster presents studies on the reactivity of the sterically less shielded FLP 2b bearing neopentyl instead of tert-butyl groups attached to aluminium.

Mes2P AlR2

Ph

2a (R = tBu)2b (R = CH2

tBu)

PhMes2P+ R2AlH

toluene1

Scheme 1: Synthesis of Al/P based FLPs via hydroalumination[1].

Treatment of the FLP 2b with trimethylsilyl azide resulted in the formation of 3 by spontaneous elimination of dinitrogen. The nitrogen atom of the resulting nitrene adduct is coordinated to aluminium and phosphorus. Two electron reduction of N-benzylidenaniline yielded 4 which has a five membered ring. Reactions with p-tolylcarbodiimide and ethylphenylketene afforded five membered heterocycles (5,6) in which the imine or carbonyl group are coordinated to the FLP via Al-O/Al-N and P-C bonds.

Ph

AlR2Mes2PNTMS

Mes2P AlR2

Ph

3

4 5

6

2b (R = CH2tBu)

TMS-N 3 / rt

- N 2

Mes2P AlR2

Ph

C NPhPh

H

Mes2P AlR2

Ph

C OCPh

EtMes2P AlR2

Ph

C NNpTol

pTol

PhN CH

Ph

Ph

C

O

Et

N C NpTol

pTol

Scheme 2: Treatment of FLP 2b with different substrates.

______________ References: [1] C. Appelt, H. Westenberg, F. Bertini, A. W. Ehlers, J. C. Slootweg, K. Lammertsma, W. Uhl, Angew. Chem., 2011, 123, 4011; Angew. Chem. Int. Ed., 2011, 50, 3925.


2 0 1 7 March 20-22


P 7

The first P-H functionalized Al/P based FLP

- Reactivity towards different functional groups - Lukas KEWELOH and Werner UHL

[email protected]

Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms Universität Münster, Germany

P

H

Mes

tBu Bis2Al-H

PBis2Al

tBuH

Mes

H

PBis2Al

tBuH

Mes

SN

tBuH2

4

Cy-N=C=N-Cy

3

1

Bis =SiMe3

SiMe3

6

NNC

5

tBu-NCS

PBis2Al

tBuH

Mes

NN

PBis2Al

tBuH

Mes

NN

Cy

H

CyH

PhPh

O

O

PBis2Al

tBuH

Mes

HO Ph

OPh

Recently we reported that hydroalumination of the secondary alkynylphosphine 1 afforded the first P-H functionalized FLP 2[1]. The P-H group represents a new functionality in FLP chemistry and leads to a unique reactivity towards heterocumulenes. 2 shows the dipolar substrate complexation similar to conventional FLPs followed by hydrogen transfer to the activated substrates. Reaction of 2 with TMS-N3 yielded the first phosphanyltriazene, in similar reactions hydrogen transfer was also observed with benzonitrile and phenylisocyanate[1]. Further examples for the unprecedented reactivity of 2 are presented in this poster. Treatment of 2 with a carbodiimide yielded compound 3 with the P-H-hydrogen shift to the terminal nitrogen atom. The reaction with a thiocyanate gave after hydrogen-shift the thiourea-derivate 4. Compared to benzonitrile cyanamide reacts similar but the transformation is much faster and gave 5 under mild reaction conditions. The dipolar complexation of benzil (6) shows that the transfer of the hydrogen atom to the activated substrates is not observed in all cases, which may depend on the low basicity of carbonyl oxygen atoms. References: [1] L. Keweloh, H. Klöcker, E.-U. Würthwein, W. Uhl: A P-H Functionalized Frustrated Lewis Pair: New FLP Reactivity with Substrate Activation and Selective Hydrogen Transfer; Angew. Chem., 55, (2016), 3212.


2 0 1 7 March 20-22


P 8

SYNTHESIS AND REACTIONS OF A PHOSPHAALKENYL SUBSTITUTED THIAZOLE-2-THIONE

Imtiaz Begum1, Rainer Streubel2 e-mail: [email protected]

Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn,

Gerhard Domagk-str.1, 53121 Bonn, Germany

Thiazol-2-thiones and their derivatives have tremendous potential in various fields including their medicinal and biological usage.[1] They also represent interesting precursors for NHCs and, hence, can be considered as versatile ligands in metal coordination chemistry.[2]

Herein we present the stepwise synthesis of 6-{(diethylamino)diphenylmethyl}phosphanyl thiazole-2-thione (II). Complex III was obtained by scrambling reaction of II with PCl3 and subsequent reaction with W(CO)5MeCN. Upon deprotonation of III, the phosphaalkene com-plex was detected by 31P NMR spectroscopy, but dimerized to afford complex IV. NMR, MS and X-ray data of all compounds will be discussed.[3]

S

N

S

Me

PC

CP

S

N

S

PhPh

Me

PhPh W(CO)5

(CO)5W

DBU

II

S

N

S

Me

P

NEt2

CH

Ph

Ph

S

N

S

Me

S

N

S

Me

P

Ph

Ph

W(CO)5

P

Ph

Ph

Cl

(OC)5W

III

IVI

S

N

S

Me

Key words: Thiazole-2-thione, Phosphane, Phosphaalkene

References: [1] D. Havrylyuka, L. Mosulaa, B. Zimenkovskya O. Vasylenkoc, A. Gzella , R. Lesyka, Eur. J. Med. Chem. 45 (2010) 5012-5021.

[2] a) A. J. Arduengo III, J. R. Goerlich, W. J. Marshall, Liebigs Ann./recueil, (1997), 365-374; b) I. Begum, G. Schnakenburg, R. Streubel, Eur. J. Inorg. Chem. 33 (2016) 5265-5270.

[3] I. Begum, G. Schnakenburg, D. P. Gates, R. Streubel, to be submitted.



2 0 1 7 March 20-22


P 9

STUDY ON THE SYNTHESIS OF P-CPh3 SUBSTITUTED SPIROOXAPHOSPHIRANE COMPLEXES

Philip Junker, Rainer Streubel*

e-mail: [email protected] and [email protected]

Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn Gerhard-Domagk-Str. 1, D-53121 Bonn, Germany

Spiroheterocycles, e.g., based on epoxides (oxiranes) and/or aziridines, are present in natural products1 and, due to their interesting physical properties,3 have been studied intensively by experimentalists as well as theoreticians.2 In contrast, the field of phosphorus-containing spiroheterocycles is largely undeveloped. Especially small-sized ring systems, having a higher ring strain, are becoming increasingly interesting as polymer precursors. In 2012 Li/Cl phosphinidenoid complexes4 were employed for the first time in the synthesis of [3,n]-spirooxaphosphirane complexes having the P-Cp* substituent. But the formation of complexes with the [3,4]-spiro ring represented a synthetic challenge as they could not be isolated and/or fully characterized.

O

E PO

E

CPh3(OC)5WP

(OC)5W CPh3

Cl

[Li(12-crown-4)(thf)n]

PH O

CPh3(OC)5W

O

n

n

n = 1,2 E = O,CH2

14,5 2,3

Herein, a study on steric effects of a sterically more demanding P-substituent (R = CPh3) on the formation of spirooxaphosphirane complexes 2,3 is reported (Scheme), focusing on ketones with and without an additional oxygen atom in the ring; X-ray structures as well as NMR data will be reported. Furthermore, the effect of different ring sizes (4-6) of the em-ployed ketones was studied.

Key words: Phosphinidenoid, Spirooxaphosphirane, Spiroheterocycles References: [1] (a) F. Perron, K. F. Albizatu, Chem. Rev. 89 (1989) 1617. (b) C. K. Heathcock, S. L.

Graham, F. P. Palvac, C. T. White, Total Synthesis of Natural Products Wiley, New York, 264, 1983.

[2] A. de Meijere, S. I. Kozhushkov, Chem. Rev. 100 (2000) 93.

[3] (a) R. Pudzich, T. Furhmann-Lieker, J. Salbeck, J. Adv. Polym. Sci. 199 (2006) 83. (b) R. Gleiter, H. Hoffmann, H. Irngartinger, M. Nixdorf, Chem. Ber. 127 (1994) 2215. (c) B. S. Lukyanov, M. B. Lukyanov, Chem. Heter. Comp. 41 (2005) 281.

[4] R. Streubel, E. Schneider, G. Schnakenburg, Organometallics 31 (2012) 4707-4710.




2 0 1 7 March 20-22


P 1 0

1,1’-BIFUNCTIONAL AMINOPHOSPHANE COMPLEXES: N/P MONO FUNCTIONALIZATIONS

Alexander Schmer, Andreas W. Kyri and Rainer Streubel*

e-mail: [email protected] and [email protected]

Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Straße 1, 53121 Bonn, Germany

Phosphinidenoids1 have neither been isolated nor observed spectroscopically, although they have been considered as key intermediates in the formation of diphosphenes.2 In contrast, Li/Cl phosphinidenoid complexes such as I became available by a facile and mild synthetic route at low temperatures3 which subsequently served as starting point for the reaction with different amines thus yielding 1,1’-bifunctional aminophosphane complexes II, selectively (Scheme).4

- [Li(12-crown-4)]Cl

P

Cl

CPh3(OC)5WP

N

CPh3(OC)5W

HNHR2

[Li(12-crown-4)(solv.)]

H/R

H/R

P

N

CPh3(OC)5W

H Me

Me3Si

P

N

CPh3(OC)5W

Me Me

Me

P

N

CPh3(OC)5W

allyl

HPh2HC

I II IV

III

V Herein, investigations on the scope of this new synthetic method to 1,1’-bifunctional

aminophosphane complexes II is presented, i.e., the formal N-H insertion reaction using Li/Cl phosphinidenoid tungsten(0) complex I and a variety of sterically and electronically different amines and ammonia. Additionally, reactivity studies of aminophosphane complexes II are presented including reaction with bases, acids, electrophiles and oxidative single electron transfer (SET) reagents thus furnishing new N- and P-derivatives, i.e., complexes III-V.5

Key words: Phosphinidenoid complexes, Aminophosphane complexes, N-H bond insertion References: [1] (a) M. Yoshifuji, I. Shima, N. Inamoto, K. Hirotsu, T. Higuchi, J. Am. Chem. Soc. 103 (1981) 4587–4589. (b) M. Yoshifuji, J. Chem. Soc., Dalton Trans. (1998) 3343–3350. [2] L. Weber, Chem. Rev. 92 (1992) 1839–1906. [3] A. Özbolat, G. von Frantzius, J. M. Pérez, M. Nieger, R. Streubel, Angew. Chem. Int. Ed. 46 (2007) 9327–9330. [4] P. K. Majhi, A. W. Kyri, A. Schmer, G. Schnakenburg, R. Streubel, Chem. Eur. J. 22 (2016) 15413–15419. [5] A. Schmer, A. W. Kyri, G. Schnakenburg, R. Streubel, submitted.




2 0 1 7 March 20-22


P 1 1

Reduction of aromatic ketones by in-situ generated Pd(II) complexes with different phosphine ligands

Éva Andrea Molnár, Luiza Ioana Gaina, Gal Emese, Luminita Silaghi-Dumitrescu


Babeş-Bolyai University, Faculty of Chemistry and Chemical Engineering, The Research Center on Fundamental and Applied Heterochemistry (METALOMICA)

Phenothiazine ligands with diphenylphosphanyl groups are good candidates for the

preparation of transition metal complexes not only with catalytic properties but also with

biological activity. The first examples of phenothiazine-based ligands containing phosphorus

were reported by S. P. Ivonin and co-workers, the products phosphorus (V) ligands, were

obtained by the reaction of 10-methyl-phenothiazine with phosphorus tribromide [1].

The diphenylphosphino-phenothiazines were prepared by lithiation of the

corresponding bromo-10-alkyl-phenothiazine. The coordination towards transition metals (Pd,

Pt) and the biological activity were studied and reported [2]. Hydrogenation of aromatic and

α,β-unsaturated aromatic ketones mediated by the palladium complexes of different

phenothiazinyl/pyridine-phosphine ligands were studied. The catalyst generated in situ from

palladium acetate and hemilabile ligand reduced the C-C and C-O double bonds. O

O

R

RHetAr

O

RHetAr∗OH

RHetAr+

∗OH

R

S

N

P PhPh

S

P

N

P N P PhPh

O

cat., Pd(OAc)2

IPA, H2, 1.5

bar

cat.:

Scheme 1.Reduction of C-C and C-O double bonds in presence of diphenylphosphino

ligands Key words: bis-phosphine ligands, phenothiazine, hydrogenation reaction, catalysis. References: [1] S. P. Ivonin, S. D. Kopteva, V. N. Serdyuk, A. A. Tolmachevand A. M. Pinchuk, Heteroat. Chem., 2001, 12, 652–657.

[2] I. H. Filip, E. Gál, I. Lupan, M. Perde-Schrepler, P. Lönnecke, M. Surducan,L. I. Găină, E. Hey-Hawkinsd and L. Silaghi-Dumitrescu, Dalton Trans., 2015, 44, 615–629.


2 0 1 7 March 20-22


P 1 2

DESIGN OF HELICENES AND π-CONJUGATED STRUCTURES WITH EMBEDDED BENZOPHOSPHOLE UNITS

Nicolas D’Imperio1, Silvia Cauteruccio2, Emanuela Licandro2, Andreas Orthaber1, Sascha

Ott1. e-mail: [email protected], [email protected].

1Department of chemistry, Angstrom Laboratories, Uppsala University, Uppsala, Sweden. 2Department of chemistry, University of Milan, Milan, Italy.

A plethora of conjugated systems have already been described as organic chemistry provides an almost infinite pool of synthetic approaches toward structural variations. However, it is striking that only a limited number of basic building blocks are commonly used. The most widely used synthons include “all carbon moieties” such as olefins, acetylenes, aromatic rings and aromatic heterocyclopentadienes, mainly thiophene and pyrrole. The introduction of novel building blocks is clearly a basis for further tailoring these π-conjugated systems. The challenge is not just simply to prepare new series of conjugated materials, but to introduce synthons that exhibit properties that the already well-established building blocks do not possess, to obtain innovative molecular architectures or unique electronic properties. This approach is nicely illustrated by exploring the suitability of organophosphorus building blocks for the tailoring of π-conjugated systems [1]. In this emerging field, π-conjugated benzophosphole derivatives are receiving attention as new phosphorus-containing materials for use in organic electronics [2]. Considering the growing interest of the scientific world about phosphorus based materials, the present work is focused on the design and synthesis of a new series of π-conjugated structures based on the benzophosphole unit (Fig. 1).

P P PhEE

Ph

R1 R1

P P PhEE

Ph

R1 R1

PEPh

PE Ph

E =

O, S, BH3.

R1 =

Ph, H, n-Bu.

(Fig. 1: Designed structures).

Several Cross-Coupling reactions (Suzuki-Miyaura, Stille, Heck and Sonogashira) were planned as a potential way for the synthesis of those π-conjugated systems starting from known building blocks [3].

Key words: (benzophosphole, cross-coupling reactions, helical structures, π conjugation)

References: [1] M. Stolar, T. Baumgartner, Chem. Asian. J. 9 (2014) 1212-1225.

[2] Y. Matano, Y. Motegi, S. Kawatsu, Y. Kimura, J. Org. Chem. 80 (2015) 5944-5950.

[3] Y. Hayashi, Y. Matano, K. Suda, Y. Kimura, Y. Nakao, H. Imahori, Chem. Eur. J. 18 (2012) 15972-15983.



2 0 1 7 March 20-22


P 1 3

Unique reactivity of C,C-diacetylenicphosphaalkenes towards acetylene addition

Muhammad. Anwar. Shameem, Andreas Orthaber* e-mail: ([email protected])

Molecular Biomimetics; Molecular Inorganic Chemistry, Department of Chemistry

Ångström laboratories Uppsala University, Sweden

Grafting of heteroatoms other than carbon in cross conjugated frameworks significantly modify their optical properties; correspondingly facilitate coordination site for the Lewis acids.[1] [2] [3] Recently our group has shown sequential introduction of acetylenic moieties on Phosphaalkene, firslty via sulfonyl acetylenic coupling followed by a Sonogashira coupling. This approach provide full stereo-chemical control and open synthetic route to create complex molecular systems with high potential in the field of molecular electronics.[4] Surprisingly investigation of this novel approach reveal very unique reactivity of the C,C diacetylenic phosphaalkene towards acetylenes. Trans acetylenic moiety is activated toward addition of phenyl acetylene in the presence of Pd[0], CuI and a suitable base. This supervene product has been fully characterized by 1H-NMR, 13C-NMR and X-ray crystallography. Preliminary investigation by 31P-{H}-NMR indicate intermediary complexation of Pd[0]. Detail investigation of mechanistic steps towards this unique reactivity is currently under progress.

Key words: Phosphaalkene, cross conjugated, acetylene. References:

[1] X.-L. Geng, S. Ott, Chem. – Eur. J. 2011, 17, 12153–12162. [2] M. A. Shameem, A. Orthaber, Chem. – Eur. J. 2016, 22, 10718–10735. [3] A. Orthaber, H. Löfås, E. Öberg, A. Grigoriev, A. Wallner, S. H. M. Jafri, M.-P. Santoni, R.

Ahuja, K. Leifer, H. Ottosson, et al., Angew. Chem. Int. Ed. 2015, 54, 10634–10638. [4] M. A. Shameem, K. Esfandiarfard, E. Öberg, S. Ott, A. Orthaber, Chem. – Eur. J. 2016, 22,

10614–10619. Acknowledgement: Swedish research council (Vetenskapsrådet), Lars Hiertas Memorial Funds, Olle Engkvist foundation, EU-COST CM1302 (SIP)


2 0 1 7 March 20-22


P 1 4

P-mediated Stereo-selective Reductive Coupling of Two Aldehydes to Unsymmetrical E-Alkenes

Juri Mai1, Keyhan Esfandiarfard1, Sascha Ott*1

e-mail: [email protected] 1Uppsala University, Department of Chemistry, Ångström Laboratory, Uppsala, Sweden

Herein, we present a new methodology for the direct formation of unsymmetrical disubstituted E-alkenes from an intermolecular reductive coupling of two different aldehydes. In comparison to the McMurry coupling[1], this new one-pot reaction is transition metal free, and proceeds under mild reaction conditions at room temperature within few minutes. It allows the formation of exclusively E-alkene products with an unsymmetrical substitution pattern in high overall yields. The selectivity is achieved by a sequential ionic mechanism wherein a first aldehyde reacts with a phosphanyl-phosphonate[2] reagent 1 to form a phosphaalkene intermediate, which can be activated by hydroxide, and generates with a second equivalent of aldehyde the olefinic product. The aldehydes can bear aromatic, heteroaromatic and aliphatic substituents R1 and R2. In future work it will be investigated, if further carbonyl group containing substrates other than aldehydes, e.g. ketones, esters, amides or ketenes, show a similar reactivity towards the phosphanylphosphonate reagent 1, and can be applied for the direct production of C=C double bond containing compounds. Key words: phospha-Horner-Wittig reagent, olefination, unsymmetrical E-alkenes, stereo-selective, one-pot synthesis

Acknowledgment: Financial support from the Swedish Research Council is gratefully acknowledged. References: [1] J. E. McMurry, Chem. Rev. 89 (1989) 1513-1524.

[2] K. Esfandiarfard, A. I. Arkhypchuk, A. Orthaber, S. Ott, Dalton Trans. 45 (2016), 2201-2207.


2 0 1 7 March 20-22


P 1 5

STUDYING THE MECHANISM OF C-O CLEAVAGE IN LIGNIN MODEL COMPOUNDS BY RUTHENIUM-XANTPHOS CATALYSTS

Rebecca C. How1, Luke Shaw1, D. M. Upulani, K. Somisara1, Paul. C. J. Kamer1

e-mail: [email protected] 1University of St Andrews, St Andrews, KY16 9ST, United Kingdom

Lignin is an aromatic non-ordered polymer that gives plants their structural rigidity by acting as a resin. Lignin-based biomass is considered as one of the most promising resources for the sustainable production of energy and chemicals.1 Due to the unique and complicated structure of lignin, simplified model compounds are tested in catalysis.2 For example, 2-phenoxy-1- phenylethanol (1) mimics the β-O-4 linkage, which is the most commonly found linkage in lignin.

OO

OOH

Me

O OH

+

Ru(H)2(CO)(PPh3)3ligand

xylenes, 135 °C, 1.75 h

1

4

32

X

PPh2 PPh2

OPAr2 PAr2

Ar = RXantphos-type ligands

O

Scheme 1: Ruthenium-catalysed C-O bond cleavage of model lignin.3

Using a variety of Xantphos-type diphosphine ligands, we investigated the effect of the bite-angle (changing X) and electronic properties (changing R) of the ligands, on the cleavage of the lignin model substrate 1.3 It was found that the optimum bite angle was 111°, as both smaller and larger bite angles gave lower reactivity. Electron-donating groups (R = OMe) were also demonstrated to give enhanced catalytic activity, whereas electron-withdrawing groups led to a decrease. This indicated that the rate determining step may be the oxidative addition of the substrate to the metal center, due to the stabilisation of higher oxidation states by more sigma donating ligands, and was confirmed by further kinetic studies.

A number of in situ studies are also currently ongoing to determine different ruthenium species throughout the catalytic cycle. This is achieved using 31P and 1H NMR to show changes in the catalyst complex throughout the reaction.

Key words: catalysis, lignin, xantphos, diphosphine, ligands References: [1] J. Zakzeski, P. C. A. Bruijnincx. A. L. Jongerius, B. Weckhuysen, Chem. Rev., 110, (2010), 3552-3599.

[2] J. M Nichols, L. M. Bishop, R. G. Bergman, J.A. Ellman, J. Am. Chem. Soc. 132, (2010), 12554-12555.

[3] L. Shaw, D. M. Upulani K. Somisara, R. C. How, N. J. Westwood, P. C. A. Bruijnincx, B. M. Weckhuysen, P. C. J. Kamer, Catal. Sci. Technol., (2017), DOI: 10.1039/C6CY00518G.


2 0 1 7 March 20-22


P 1 6

Synthesis of 2-Trimethylsilylphosphinines: [4+2]-Cycloaddition of 2-Pyrones with Trimethylsilylphosphaalkynes

Friedrich Wossidlo, Marija Habicht, Christian Müller e-mail: [email protected], C.Mü[email protected]

Institute of Chemistry and Biochemistry, Freie Universität Berlin, 14195 Berlin, Germany

Phosphinines are the phosphorus analogs of pyridines, while the unsubstituted phospinine shows 88% of the aromatic stabilization energy of benzene. The phosphorus atom carries a partially positive charge and shows very low basicity. The LUMO is significantly lower in energy than the LUMO of pyridines and has a large coefficient at the phosphorus. The differences of the electronic properties make phosphinines better π-acceptor but weaker σ-donor ligands than pyridines.[1]

Phosphinins can be synthesized by various methods. Our work based on the research of Regitz et al.. They were able to synthesize 2-tert-butylphosphinines by [4+2]-cycloaddition of 2-pyrone with tert-butylphosphaalkyne.[2] The application of this reaction is restricted by the stability of the phosphaalkyne. However, we could show that the literature-known trimethylsilylphosphaalkyne[3] can be used in this reaction as well and some 2-trimethylsilylphosphinines could be synthesized in this way.[4] These can be further modified, for example, by means of C-C-coupling or protodesilylation reactions.

O O

O O

Br

O OPh

Ph

O OCl

O O

D

P SiMe3

P SiMe3

Ph

Ph

P SiMe3Br

P SiMe3Cl

P SiMe3

H/DH/D

Me3Si C P- CO2

Key words: low-coordinate phosphorus compounds, phosphinine, phosphaalkyne, [4+2]-cycloaddition, phosphorus heterocycle

References: [1] F. Mathey, Phosphorus-Carbon Heterocyclic Chemistry, Elsevier Ltd., 766, 2001.

[2] W. Rösch, M. Regitz, Z. Naturforschung B 41 (1986) 931–933.

[3] S. M. Mansell, M. Green, R. J. Kilby, M. Murray, C. A. Russell, C. R. Chimie 13 (2010) 1073–1081.

[4] M. Habicht, F. Wossidlo, M. Weber, C. Müller, Chem. Eur. J. 22 (2016) 12877–12883.


2 0 1 7 March 20-22


P 1 7

NEW REACTIONS OF PHOSPHINITO COMPLEXES

Robert Kunzmann1, Rainer Streubel1 e-mail: [email protected]

1Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Straße 1, 53121 Bonn, Germany

The synthetic potential of phosphinito complexes remained unnoticed after they were

firstly discovered in 2012.1 After a new synthetic route to this class of phosphane complexes was reported, the complex was used to synthesize unprecedented phosphane complexes with a P-O-B motif.2,3 This class of complexes reveiled to be a key to molecular complexes having a very interesting reactivity: deprotonation led to the Li/OR phosphinidenoid complex I which turned out to be the first example of a molecular anionic FLP complex II reacting readily with CO2 in a selective and concerted manner.3

(OC)5W

P

CH(SiMe3)2

OBCy2

[K(18-crown-6)]+

(OC)5W

P

CH(SiMe3)2

O OBCy2

OO[K(18-crown-6)]

+CO2

Et2O

I II Herein, synthesis of new 1,1’-bifunctional phosphane complexes having other P-O-E

linkages III as well as new Li/OR phosphinidenoid complexes IV will be presented. First results on reactions of complexes IV with cumulenes such as PhNCO, will be presented.4

(OC)5W

P

CH(SiMe3)2

H OERnClm-1

KHMDS18-crown-6

- HMDS

(OC)5W

P

CH(SiMe3)2

OERnClm-1

[K(18-crown-6)]+

III IVE = Si, Ge, Sn

Key words: anionic FLP, carbon dioxide, phosphinidenoid, phosphinito

References: [1] L. Duan, G. Schnakenburg, J. Daniels, R. Streubel, Eur. J. Inorg. Chem. 21 (2012) 3490-3499.

[2] A. W. Kyri, G. Schnakenburg, R. Streubel, Chem. Commun. 52 (2016) 8593-8595.

[3] A. W. Kyri, R. Kunzmann, Z.-W. Qu, S. Grimme, G. Schnakenburg, R. Streubel, Chem. Commun. 52 (2016) 13361-13364.

[4] R. Kunzmann, G. Schnakenburg, R. Streubel, to be published.



2 0 1 7 March 20-22


P 1 8

INVESTIGATING THE SYNTHESIS OF 5-PHOSPHASEMIBULLVALENES:

AN EXPERIMENTAL AND THEORETICAL STUDY

Massimo Rigo, Christian Müller* e-mail: [email protected], [email protected]

Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstraße 34/36, 14195 Berlin, DE

During our intensive research on phosphinines and the related phosphabarrelenes,[1]

we recently discovered that phosphabarrelenes can undergo a quantitative photochemical di-π-methane rearrangement towards 5-phosphasemibullvalenes.[2] This hitherto unknown conversion of unsaturated phosphorus compounds leads to configurationally stable, chiral products as proven by means of HPLC analysis and X-ray diffraction.

The proposed mechanism for the di-π-methane rearrangement and the selectivity of the reaction were confirmed experimentally and by means of DFT calculations, and we were able to structurally characterize a number of 5-phosphasemibullvalene derivatives, extending the substrate scope of this reaction to differently substituted phosphabarrelenes. Some of the obtained derivatives present interesting optical properties. Moreover several derivatives have been tested as ligands in the gold-catalyzed cycloisomerization of propargyl amide.

These preliminary investigations pave the way for the use of these compounds as ligands in (asymmetric) homogeneous catalysis and for phosphorus-containing molecular materials.

Key words: di π-methane rearrangement, heterocycle, chiral ligands, fluorescence, DFT calculations

References: [1] M. Rigo, J. Sklorz, N. Hatje, , M. Weber, J. Wiecko, C. Müller, Dalton Trans. 2016, 2218. [2] M. Rigo, M. Weber, C. Müller, Chem. Commun. 2016, 7090.


2 0 1 7 March 20-22


P 1 9

A convenient route to mixed pnictogenylboranes

Oliver Hegen, and Manfred Scheer e-mail: [email protected]

Institute of Inorganic Chemistry, University of Regensburg, Regensburg, Germany

Donor stabilized pnictogenylboranes are valuable precursors for the synthesis of oligomeric and polymeric compounds.[1,2] In comparison to carbon based polymers, it was not possible to synthesize copolymers composed by different (substituted) pnictogenatoms and boron in their backbone yet.[3] A convenient route was developed to synthesize mixed pnictogenylboranes, which are stabilized through a Lewis acid and base. It was possible to gain access to the first molecules with a neutral P-B-As-B- and P-B-Sb-B-sequence. These compounds might be used as precursors for copolymers and longer Group 13/15 catena compounds.

Keywords: Boron, Phosphorus, Arsenic, Antimony, Polymer References: [1] A. C. Malcolm, K. J. Sabourin, R. McDonald, M. J. Ferguson, E. Rivard, Inorg. Chem. 51 (2012) 12905.

[2] C. Marquardt, T. Jurca, K.-C. Schwan, A. Stauber, A. V. Virovets, G. R. Whittell, I. Manners, M. Scheer, Angew. Chem. Int. Ed. 54 (2015) 13782.

[3] A. Staubitz, A. P. M. Robertson, M. E. Sloan, I. Manners, Chem. Rev., 110 (2010), 4023.


2 0 1 7 March 20-22


P 2 0

[4+2]-Cycloaddition Reactions with 3H-1,2,3,4-Triazaphospholes: A New and Elegant Route to Diazaphospholes

Martin Papke1, Christian Müller1

e-mail: [email protected], [email protected] 1 Institut für Chemie und Biochemie, Freie Universität Berlin,

Fabeckstr. 34/36, 14195 Berlin, Germany.

The uncatalyzed and regioselective formation of 3H-1,2,3,4-triazaphospholes by a 1,3-dipolar cycloaddition reaction between organic azides and phosphaalkynes has been well investigated over years.[1,2,3] We could recently observe that the aromatic triazoles are not able to undergo [4+2]-cycloaddition reactions with activated dienophiles. In contrast to that, 3H-1,2,3,4-triazaphospholes can react with hexafluoro-2-butyne to CF3-substituted diazaphospholes of type C.[4] The reactive intermediate B could not be isolated prior to Retro-Diels-Alder-Reaction.

P

NNN

tBuR

+CF3F3C

Diels-Alder-Reaction

NN

PN

CF3

F3C

tBuR

Retro-

Diels-Alder-Reaction

P

NNR

CF3

CF3- tBuCN

A

B

C

This reaction was performed for mono- and polydentate pyridyl- and benzyl-based 3H-1,2,3,4-triazaphosphole derivatives. Currently, we are investigating the coordination chemistry of these unprecedented diazaphospholes with metal precursors such as Cu(I) and Rh(I). These low-coordinate phosphorus heterocycles might have interesting properties as ligands for transition-metal mediated chemical transformations.

Key words: Triazaphospholes, [4+2]-Cycloaddition, Diazaphospholes References: [1] W. Rösch, M. Regitz, Angew. Chem. Int. Ed. 23 (1984), 900.

[2] (a) L. Nyulászi, T. Vesprémi, J. Réffy, B. Burkhardt, M. Regitz, J. Am. Chem. Soc.114 (1992), 9080−9084. (b) L. Nyulászi, Chem. Rev. 101 (2001), 1229−1246.

[3] (a) J. A. W. Sklorz, S. Hoof, M. G. Sommer, F. Weißer, M. Weber, J. Wiecko, B. Sarkar, C. Müller, Organometallics 33 (2014), 511−516. (b) C. Müller, J. A. W. Sklorz, I. de Krom, A. Loibl, M. Habicht, M. Bruce, G. Pfeifer, J. Wiecko, Chem. Lett. 43 (2014), 1390–1404. c) J. A. W. Sklorz, S. Hoof, N. Rades, N. De Rycke, L. Könczöl, D. Szieberth, M. Weber, J. Wiecko, L. Nyulászi, M. Hissler, C. Müller, Chem. Eur. J. 21 (2015), 11096-11109.

[4] J. A. W. Sklorz, 3H-1,2,3,4-Triazaphospholes – Tuned 1H-1,2,3-Triazoles or Independent Ligand Class, PhD Thesis, 2016, FU Berlin.


2 0 1 7 March 20-22


P 2 1

Comparing a Frustrated Lewis pair to a Metal-Ligand Cooperation System Evi R. M. Habraken, Andreas W. Ehlers, J. Chris Slootweg*

e-mail: [email protected] [email protected]

Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, The Netherlands

The discovery of main-group systems, such as frustrated Lewis pairs, possessing a lone pair of electrons and a vacant orbital have shown to be able to activate small molecules [1]. The Lewis acid and Lewis base both undergo bond formation and cleavage processes. This too holds for metal-ligand cooperation (MLC) systems, where both the metal and ligand are involved in bond activation processes [2].

On this poster, a comparison of both systems is made, showing that the MLC system can be regarded as a FLP, where the ligand can be viewed as the Lewis base and the metal is the Lewis acid (see Scheme 1) [3].

Scheme 1 Frustrated Lewis pair (left) and metal-ligand cooperation system (right)

Key words: Frustrated Lewis pair, Metal-ligand cooperation system, Pincer, Lewis acid/base References: [1] F. Bertini, V. Lyaskovskyy, B. J. J. Timmer, F. J. J. de Kanter, M. Lutz, A. W. Ehlers, J. C. Slootweg, K. Lammertsma, J. Am. Chem. Soc. 134 (2012) 201-204

[2] C. Gunanathan, Y, Ben-David, D. Milstein, Science 317 (2007) 790-792

[3] D. W. Stephan, Org. Biomol. Chem 6 (2008) 1535-1539

BPh2tBu2P

vs N

P

P

Ru CO

HP = PiPr2

or PtBu2

Lewis base Lewis acid

P

Lewis base

Lewis acid




2 0 1 7 March 20-22


P 2 2

Coordination Chemistry of Frustrated Lewis Pairs.

Devin H.A. Boom, Andreas W. Ehlers and J. Chris Slootweg* e-mail: [email protected] [email protected]

Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands

Since the discovery in 2006 that frustrated Lewis pairs (FLPs) can heterolytically split dihydrogen[1], a new field of main-group chemistry and catalysis was born. Since then, FLPs have been reported to activate a large variety of homo- and heteronuclear bonds, which can be applied as key step in a broad range of FLP catalytic reactions.

Another remarkable application of frustrated Lewis pairs is their application as stabilizing ligands for highly reactive intermediates. In this respect, we became interested in phosphazides, which are intermediates in the Staudinger reaction that readily release dinitrogen resulting in the formation of iminophosphoranes.[2]

Here, we report on the reaction of a C1 bridged frustrated Lewis pair (tBu)2PCH2BPh2 with different organic azides that allows for the first time the detection of all three different coordination modes (A, B and C) of the intermediate phosphazides. Their formation is fully supported with DFT calculations of the complete reaction profile, which generates new insight into this essential reaction in organic chemistry.

Key words: frustrated Lewis pairs, reactive intermediates, trapping, azides References: [1] G.C. Welch, R.R. San Juan, J.D. Masuda, D.W. Stephan, Science, 314 (2006) 1124 - 1126 [2] (a) D. Bourissou, Angew. Chem. Int. Ed., 46 (2007) 3333 - 3336. (b) G. Erker, Dalton Trans., 39 (2010) 7556 - 7564. (c) G. Erker, Chem Commun., 48, (2012) 11739 - 11741. (d) W. Uhl, Eur. J. Inorg. Chem., 26 (2016) 4170 - 4178

t-Bu2P BPh2N N N

R

A frustrated Lewis pair

t-Bu2P BPh2N

NN

R

t-Bu2PN

BPh2

NNR

N NBPh2t-Bu2P

NR

(A) (B) (C)


2 0 1 7 March 20-22


P 2 3

UNPRECEDENTED PHENYLPHOSPHINIDENE TRANSFER REACTIONS FROM CARBENE-PHOSPHINIDENE ADDUCTS

Tetiana Krachko1, Mark Bispinghoff2, Hansjörg Grützmacher2, J. Chris Slootweg1

[email protected], [email protected] 1Van 't Hoff Institute for Molecular Sciences, University of Amsterdam

2Laboratory of Inorganic Chemistry, ETH Zürich

Phosphinidenes are convenient precursors for the synthesis of great variety of organophosphorus compounds.1 Although carbene adducts of phenylphosphinidene (NHC=PPh)3 have been known for more than a decade and studied in detail computationally, there are no examples that describe the transfer of the phenylphosphinidene fragment from any of the carbene-phosphinidene adducts.

Herein, we present the reactivity of MeNHC=PPh (1) toward organic electrophiles that results in phenylphosphinidene transfer reactions. We also show that the reactions can be tuned by the employment of ZnCl2 (Scheme 1). In addition, the reaction pathway of these phosphinidene transfer reactions is proposed based on DFT calculations as well as the determination of crystal structures of intermediates and products.

Scheme 1. Phosphinidene transfer reactions from MeNHC=PPh

Key words: phosphorus heterocycles, phosphinidene, carbenes, cycloadditions, density

functional calculations References: [1] J. C. Slootweg, K. Lammertsma, Science of Synthesis, Georg Thieme, Vol.42, 15─36, 2009

[2] A. Arduengo, J. C. Calabrese, A. H. Cowley, H. V. R. Dias, J. R. Goerlich, W. J. Marshall, B. Riegel, Inorg. Chem. 36 (1997), 2151-2158


2 0 1 7 March 20-22


Reactivity of Phosphinine Iron Complexes

Julia Leitl and Robert Wolf*


Institute of Inorganic Chemistry, University of Regensburg, D-93040 Regensburg, Germany

Phosphinines are used as versatile ligands in coordination chemistry due to their unique electronic and

steric properties.[1] Moreover, the attention on phosphinine complexes as pre-catalysts in homogeneous

catalysis rose since the 1990s. A variety of transition metal phosphinine complexes were applied in

catalytic reactions, such as cyclotrimerizations, hydroformylations, and hydrogenations.[2]

Here, we present a reactivity study on a reported hydro-phosphinine iron complex [Cp*FeTPP-1H] (1)[3]

which was used in hydroboration and transfer hydrogenation reactions. The first step of these reactions

is the insertion of the organic substrate into the P−H bond of 1. The yields of the corresponding product

(up to 98%) were determined by 1H-NMR spectroscopy.

In addition, our interests lie in the investigation of the reactivity of our reported phosphinine iron

complexes toward CO2. Unfortunately, 1 did not react with CO2 but the anionic iron phosphine complex

[K([18]crown-6)(thf)2][Cp*FeTPP] was able to form a CO2-fixation product.

Key words: phosphinine, hydroboration, transfer hydrogenation, CO2

References:

[1] P. L. Floch, Coord. Chem. Rev., 250 (2006) 627–681.

[2] a) H. Bönnemann, Angew. Chem. 97 (1985) 264–279. B. b) Breit, R. Winde, T. Mackewitz, R.

Paciello, K. Harms, Chem. Eur. J. 7 (2001) 3106–3121. c) Y. Miyake, E. Isomura, M. Iyoda, Chem.

Lett., 35 (2006) 836–837. d) M. T. Reetz, G. Mehler, Tetrahedron Lett., 44 (2003) 4593–4596.

[3] B. Rezaei Rad, U. Chakraborty, B. Mühldorf, J. A. W. Sklorz, M. Bodensteiner, C. Müller, R.

Wolf, Organometallics, 34 (2015) 622–635.


2 0 1 7 March 20-22

- - N a p o c a , R O M A N I A

Reactions of a Phosphinine Ferrate Complex with Electrophilic Halogenating Agents A Route to Covalent and Ionic Halo Phosphinines

Christian M. Hoidn, Robert Wolf


Institute of Inorganic Chemistry, University of Regensburg, D-93040 Regensburg, Germany

Phosphinines and the related phosphacyclohexadienyls are six-membered phosphorus

containing heterocycles showing versatile coordination behavior.[1] They bind to numerous

transition metals and were successfully applied in homogeneous catalysis.[1,2] The phosphorus

atom in phosphinines can be widely functionalized. Phosphorus halogenation is well

established for free phosphinines resulting in 5-halo phosphinines, whereas halo phosphinine

metal complexes are barely known in literature.[3]

Recently, we reported that the anionic iron complex 1 reacts readily with various electrophiles

affording a series of novel phosphacyclohexadienyl complexes.[4] As an extension of this

study we present the reaction of 1 with several electrophilic halogenating agents. Depending

on the halide, we observe the formation of unprecedented complexes comprising either

covalent (2, 3) or ionic (4, 5) halo phosphinine moieties.

Key words: Iron, Phosphinines, Halogenation, Electrophiles

References:

[1] a) P. Le Floch, Coord. Chem. Rev. 2006, 250, 627 681; b) C. Müller, L. E. E. Broeckx, I. de

Krom, J. J. M. Weemers, Eur. J. Inorg. Chem. 2013, 2013, 187 202.

[2] A. Moores, N. Mézailles, L. Ricard, P. Le Floch, Organometallics 2005, 24, 508 513.

[3] a) H. Kanter, K. Dimroth, Angew. Chem. Int. Ed. Engl. 1972, 11, 1090 1091; b) K. Dimroth, S. Berger, H. Kaletsch, Phosphorus Sulfur Relat. Elem. 1981, 10, 295 303; c) K. Dimroth, M.

Lückoff, H. Kaletsch, Phosphorus Sulfur Relat. Elem. 1981, 10, 285 294; d) M. Doux, C. Bouet,

N. Mézailles, L. Ricard, P. Le Floch, Organometallics 2002, 21, 2785 2788; e) M. Doux, N. Mézailles, L. Ricard, P. Le Floch, Eur. J. Inorg. Chem. 2003, 2003, 3878 3894.

[4] C. M. Hoidn, R. Wolf, Dalton Trans. 2016, 45, 8875 8884.


2 0 1 7 March 20-22


P 2 6

Thermolysis pathways of phosphororganics under oxidative conditions

Shuyu Liang1, Patrick Hemberger3, Joëlle Levalois-Grützmacher1, Sabyasachi Gaan2 and Hansjörg Grützmacher1

[email protected] 1Laboratory of Inorganic Chemistry, ETH Zürich, Switzerland

2Chemistry group, Empa, Swiss Federal Laboratories for Materials Science, St.Gallen, Switzerland 3Laboratory for Femtochemistry and Synchrotron, Paul Scherrer Institute, Villigen-PSI, Switzerland

This is a continuation of our previous investigation on pyrolysis of phosphororganics (PPOs).[1] The synchrotron based photoelectron photoion coincidence (iPEPICO) spectrometry technique[2] was used to probe the thermolysis mechanism of both compounds under oxidative condition. Dimethyl methyl phosphonate (DMMP) and dimethyl phosphoramidate (DMPR) were chosen as model OPCs in this study and thermalized in a specially designed micro flow reactor. Photoionization experimental data together with quantum calculation helped to identify the formation pathways of important phosphorus species associated with flame inhibition, catalytic combustion and astrochemistry, such as ∙P=O and ∙P(=O)2

[3] and P≡N [4]. The highlight of the current study is that ∙P(=O)2 is only formed under oxidative thermolysis, whereas ∙P=O (DMMP) or P≡N (DMPR) was formed mainly in an inert atmosphere [1]. It is found that oxidative condition favors the formation of ∙P(=O)2 and HOP=O. Specific pathways leading to the formation of the above mentioned phosphorus species will be discussed in detail in the presentation. A simplified pathway of DMMP/DMPR is illustrated in Scheme 1.

Scheme 1: Elucidation of the role of oxygen in promoting formation of phosphoryl species. Key words: phosphororganics, phosphoryl radicals, PN species, photoionization, intermediates References: [1] S. Liang, P. Hemberger, M. Neisius, A. Bodi, H. Grützmacher, J. Levalois- Grützmacher and S. Gaan, Chem. Eur. J. 21 (2015) 1073-1080. [2] A. Bodi; M. Johnson; T. Gerber; B. Sztáray and T. Baer, Rev. Sci. Instrum. 80 (2009), 034101, 1-7. [3] A. Twarowski, Combust. Flame 94 (1993) 91-107. [4] L. M. Ziurys, Astrophys. J. 321 (1987) 81-85.



2 0 1 7 March 20-22


P 2 7

Oxidative Degradation of White Phosphorus by a Poly-onio Substituted Selenium Oxide Dication

Fabian A. Watta, Maximilian Donatha, Chris H. Salaa, Roland Fischerb, Felix Hennersdorfa and Jan J. Weiganda*


a TU Dresden, Department of Chemistry and Food Chemistry, 01062 Dresden, Germany b TU Graz, Institute of Inorganic Chemistry, 8010 Graz, Austria

Selenium dioxide (SeO2), among other oxides, is commonly used as oxidant in organic synthesis.[1] Derivatives thereof may also be applied as versatile oxidation reagents in e.g. inorganic chemistry. Hence, the synthesis of coordination complexes from the respective metal oxides via deoxygenation reactions is of great interest.[2]

This contribution presents the synthesis of the mononuclear coordination complex 2[OTf]2 from SeO2 via deoxygenation by 1-triflyl(4-dimethylamino)pyridinium triflate (1[OTf]) in the presence of additional 4-dimethylaminopyridine (DMAP) (I). The unique bonding motif observed for cation 22+ is discussed on the basis of quantum chemical calculations.

2[OTf]2 proves to be a powerful oxidant, reacting with white phosphorus (P4) under mild conditions to give the P(V)-compound 3[OTf] as main product (II). Upon controlled hydrolysis of 3[OTf] the first example of a cyclo-selenotriphosphate ([HDMAP]3[P3Se3O6], [HDMAP]34) is obtained (III), emphasizing the possible use of 3[OTf] as a versatile [OSeP]+-transfer reagent.

SeO2 + + 3 DMAP

(I)

SeN

N N

N

ON

NN

N[OTf]2

2[OTf]2

NN Tf[OTf]

1[OTf]

PO Se

N N

N N

[OTf]

3[OTf]

(III)

OP

OPO

PSe

O O

O

SeSe

[HDMAP]3

[HDMAP]34

H2O

(II)

P4

DMAP = NNTf = SO2CF3

Key words: deoxygenation, oxidation, white phosphorus, selenophosphate

References: [1] a) G. R. Waitkins, C. W. Clark, Chem. Rev. 36 (1945) 235–289. b) M. Schröder, Chem. Rev. 80 (1980) 187–213. [2] a) H. W. Roesky, I. Haiduc, N. S. Hosmane, Chem. Rev. 103 (2003) 2579–2595. b) W. A. Herrmann, J. G. Kuchler, J. K. Felixberger, E. Herdtweck, W. Wagner, Angew. Chem. Int. Ed. 27 (1988) 394–396. c) W. A. Herrmann, F. E. Kühn, Acc. Chem. Res. 30 (1997) 169–180.

Acknowledgement: The authors thank the ERC (SynPhos 307616) for financial support as well as the Center for Information Services and High Performance Computing (ZIH) at TU Dresden for generous allocations of computational time on the Bull Cluster.


2 0 1 7 March 20-22


P 2 8

PHOSPHORUS DERIVATIVES BASED ON SULFUR-CONTAINING PINCER LIGANDS

Noémi Deak1,2, David Madec2, Gabriela Nemeş1, Luminiţa Silaghi-Dumitrescu1

e-mail: [email protected] 1Faculty of Chemistry and Chemical Engineering, Babeş-Bolyai University

str Arany Janos nr.11 , 400028, Cluj-Napoca, Romania 2Université de Toulouse, UPS, LHFA, CNRS, LHFA UMR 5069

118 Route de Narbonne, F-31062 Toulouse, France

Pincer ligands are widely known for their role in the chemistry of transition metal complexes [1] because of their versatility. These ligands were proven to be useful in the stabilization of low valent p-block elements also, for example compounds containing Ge, Sn, Sb, Bi atoms.[1,2] However, there are fewer examples of phosphorus containing derivatives supported by such ligands.[3]

In the present work sulfone and sulfoxide base pincer ligands were employed to obtain dichlorophosphine and diphenylphosphine derivatives. The stabilization effect of the ligands was evaluated.

Tol

Tol

S

S

OO

OO

P

n

nn =

0, 1

R = Cl,

Ph

R

R

Scheme 1.

The reactivity study of the obtained compounds is under further investigation. Key words: pincer-ligand, phosphorus derivatives References: [1] G. van Koten, D. Milstein, Topics in Organometallic Chemistry Volume 40:

Organometallic Pincer Chemistry, Springer, 2013; G. van Koten, R.A Gossage, Topics in Organometallic Chemistry Volume 54: The Privileged Pincer-Metal Platform: Coordination Chemistry & Applications, Springer, 2016.

[2] N. Deak, P.M. Petrar, S. Mallet-Ladeira, L. Silaghi-Dumitrescu, G. Nemeş, D. Madec, Chem. Eur. J. (2016) 22, 1349-1354.

[3] T. Reznicek, L. Dostal, A. Ruzicka, R. Jambor, Main Group Met. Chem. (2012) 35, 129-133.


2 0 1 7 March 20-22


P 2 9

Pt-CATALYSED HYDROPHOSPHINATION AS A ROUTE TO DIPHOSPHINES

Ailis Chadwick, Martin Heckenast, Paul Pringle


School of Chemistry, University of Bristol, Cantock’s Close, Bristol, BS8 1TS.

Hydrophosphination, the addition of a P‒H bond across a multiple bond, may be achieved by a variety of routes including acid- or base-catalysis, and radical initiation. 1 However, of the large number of methods possible, transition metal-catalysis provides an opportunity to combine high atom‒efficiency with selectivity to create new phosphorus‒carbon bonds.2 Platinum(0)‒catalysed hydrophosphination of activated alkenes offers access to functionalized phosphines that have proved useful as ligands for homogeneous catalysis.3 This process was first reported in 1990 when it was shown that addition of acrylonitrile to PH3 occurred in the presence of a platinum(0) catalyst.4 Investigations into the mechanism of platinum(0)‒catalysed hydrophosphination have focused on the synthesis of monophosphines.5 Surprisingly, despite the possibility of catalyst poisoning by substrate chelation, functionalized diphosphines can also be prepared via this method.6 Here we demonstrate an efficient and selective hydrophosphination of unsymmetrical diphosphine 1 and investigate the mechanism of the transformation.

Key words: hydrophosphination, platinum(0), catalysis, diphosphines [1] E. Costa, P. G. Pringle, B. Smith and K. Worboys, J. Chem. Soc., Dalt. Trans., (1997), 4277–4282. [2] M. Espinal-Viguri, A. K. King, J. P. Lowe, M. F. Mahon and R. L. Webster, ACS Catal., 6, (2016), 7892–7897. [3] D. K. Wicht, I. V Kourkine, B. M. Lew, J. M. Nthenge, D. S. Glueck, J. Am, Chem. Soc., 7863, (1997), 5039–5040. [4] P. G. Pringle and M. B. Smith, J. Chem. Soc. Chem. Commun., (1990), 1701–1702. [5] C. Scriban, I. Kovacik and D. S. Glueck, 24, (2005), 4871–4874. [6] I. Kovacik, C. Scriban and D. S. Glueck, Organometallics, 25, (2006), 536–539.

PH3 CN+NC CNP

Pt(norbornene)3

CN

P PH2 CO2Me+

CO2Me

CO2MePP Pt(norbornene)3

1


2 0 1 7 March 20-22


P 3 0

Effect of phosphacycle ring size on hydroformylation catalysed by Rh-diphosphites

Alexandra M. Miles-Hobbs, Tom Young, Paul G. Pringle [email protected]

University of Bristol, Cantock’s Close, Bristol, BS8 1TS

Phosphites have attracted great interest as ligands for homogeneous catalysis.1 In particular, complexes of cyclic phosphites have demonstrated high activities as catalysts in processes such as hydroformylation (e.g. 1),2 hydrocyanation3 (e.g. 2) and asymmetric hydrogenation (e.g. 3).4

The phosphites of marked interest contain a 7-membered phosphacycle derived from 2,2’-biphenol. However, to our knowledge, ligands containing the smaller 6-membered phosphacycle derived from 1,8-dihydroxynaphthalene have not been investigated as potential ligands for catalysis. The diphosphite ligand 4 has been synthesised and its chemistry explored.

Hydroformylation of alkenes is arguably the most significant industrial application of homogeneous catalysis today. A comparison of results of the hydroformylation of 1-hexene catalysed by Rh complexes of the novel ligand 4 and the analogous ligand 1 will be presented; the effect of phosphite ring size will be discussed. Key words: diphosphite, hydroformylation, 6-membered phosphacycle References: [1] A. Gual, C. Godard, V, de la Fuente, S, Catsillón, Phosphorus (III) Ligands in Homogeneous Catalysis, John Wiley & Sons, Ltd., 81–131, 2012.

[2] J. M. Mayer, J. E. Babin, E. Billig, D. R. Bryant, T.W. Leung, US Patent, US 5288918 A, 1994.

[3] M. J. Baker, K. N. Harrison, A. G. Orpen, P. G. Pringle, G. Shaw, J Chem. Soc., Chem. Commun., (1991), 803-804.

[4] M. T. Reetz, G. Mehler, Angew. Chem., Int. Ed., 39, (2000), 3889-3890.

O OP POO O

OR1R1

R2R2

R1 = tBu, R2

= OMe (1)R1

= R2 = H (2)

OP

OOR

3

O OPO

OP

O

O

4


2 0 1 7 March 20-22


P 3 1

NOVEL ANIONIC COBALT-TETRAPHOSPHIDO-COMPLEXES

Thomas M. Maier1, Stefan Pelties1, Dirk Herrmann1, Robert Wolf 1 e-mail: [email protected], [email protected]

1University of Regensburg, Institute of Inorganic Chemistry, Universitätsstraße 31, 93053 Regensburg, Germany

Transition metal tetraphosphido complexes generated from white phosphorus (P4) or other P4-sources could serve as intermediates for an environmentally friendly access to new polyphosphorus compounds.1

Herein, we present the synthesis of different tetraphosphido complexes starting from heteroleptic α-diimine-cobaltate 1 bearing the redoxactive α-diimine ligand ArBIAN (Ar = Dipp (2,6-diisopropylphenyl), Mes (2,4,6-trimethylphenyl); BIAN = bis(arylimino)acenaphthene) and the labile ligand 1,5-COD. The electronically flexible BIAN-ligand is capable to either store or release electrons and acts thereby as an electron reservoir.2

The reactions with P4 and [(Dippnacnac)Ga(P4)] (Dippnacnac = CH[CMeN(2,6-iPr2C6H3)]2), respectively, afforded the new anionic tetraphosphido complexes 2, 3, and 4 with slightly different P4-moieties (Figure 1). Compounds 3 and 4 represent the first known complexes with a P4-unit between cobalt and gallium and are potentially useful for further functionalizations with electrophiles.

The cyclovoltammetric characterization of 2 encouraged to isolate its detected monoanionic as well as its neutral tetraphosphido-complex by selective oxidation with [Cp2Fe]BArF

4.3

N NR RCo

[K(solv]+

2

2 [K(thf)2]+

N

N

R

R

CoN

N

R

R

CoP

PP

P

N

N

R

R

Co GaPP

P

PN

N

Dipp

Dipp

-

P4 Dipp

Dipp

NN Ga

P

P P

P

R = Dipp (3), Mes (4)R = Dipp (2) 1

[K(dme)x]+

- 1,5-COD- 1,5-COD

Figure 1. Reactivity of 1 toward P4 and [(Dippnacnac)Ga(P4)].

Key words: Tetraphosphido, Cobalt, Gallium, Metalate, α-Diimine References: [1] a) B. M. Crossairt, N. A. Piro, C. C. Cummins, Chem. Rev. 110 (2010) 4164. b) M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini, Chem. Rev. 110 (2010) 4178. c) M. Peruzzini, L. Gonsalvi, A. Romerosa, Chem. Soc. Rev. 34 (2005) 1038. d) M. Peruzzini, R. Abdreimova, Y. Budnikova, A. Romerosa, O. J. Scherer, H. Sitzmann, J.Organomet. Chem. 689 (2004) 4319. [2] P. Chirik, K. Wieghardt, Science 327 (2010) 794-795. [3] S. Pelties, T. Maier, D. Herrmann, B. de Bruin, C. Rebreyend, S. Gärtner, I. G. Shenderovich, R. Wolf, Chem. Eur. J. doi: 10.1002/chem.201603296.


2 0 1 7 March 20-22


P 3 2

INTRAMOLECULAR NUCLEOPHILIC SUBSTITUTION IN ω-HALOALKYLPHOSPHINE DERIVATIVES Paweł Woźnicki1, Ewelina Korzeniowska1, Marek Stankevič1

e-mail: [email protected] 1Department of Organic Chemistry, Faculty of Chemistry, Maria Curie-Sklodowska University,

Gliniana St. 33, Lublin 20-614

Organophosphorus compounds are one of the main groups of ligands used in reactions catalyzed by transition metal complexes.[1] Among them cycloalkyl and P-heterocyclic phosphines constitute an important subgroup with good σ-donating ability and medium to high steric hindrance which makes them suitable for transformations of less activated or deactivated substrates.[2]

We have developed a method of the synthesis of cyclic phosphines through haloalkylation of simple secondary or tertiary phosphine derivatives followed by α-metallation and intramolecular nucleophilic substitution of halide at the terminal carbon atom. This gives an easy access to a variety of cyclic phosphines or phosphines with a cycloalkyl substituent. The use of a chiral base such as butyllithium-sparteine complex could lead to the formation of chiral non-racemic cycloalkylphosphine analogues.

PhPS 1. s-BuLi,

(+)

-sparteine2. MeI

Et2O PhPS

PhPS

89% ee 89%

ee

Ar PX

Ar PX

ClAr P

X

Ar PX

R R R

R

( )n

( )n(

)n

1. base2. electrophile base

R' = H, MeX

= S, BH3

Ar = Ph, o-Tol,

p-Tol o-An, 1-naphthyl

R =

Ar, Me, Et

Key words: alkylation, cyclization, deprotonation, phosphine, stereoselective synthesis Financial support from National Science Centre (grant No 2012/07/E/ST5/00544) is kindly

acknowledged. References:

[1] a) R. J. Lundgren, M. Stradiotto, Chem. Eur. J., 18 (2012), 9758 – 9769; b) P. G. Gildner, T. J. Colacot, Organometallics, 34 (2015), 5497–5508

[2] (a) T. Ishiyama, K. Ishida, N. Miyaura, Tetrahedron, 57 (2001), 9813–9816; b) D. Zim, V. R. Lando, J. Dupont, A. L. Monteiro, Org. Lett., 3 (2001)


2 0 1 7 March 20-22


P 3 3

INVESTIGATION OF PHOSPHINE COMPLEX DEPOSITED ON ZnO NANOROD SUBSTRATE FOR WATER SPLITTING

Fatih Tezcan, Asad Mahmood, Gülfeza Kardaş e-mail: [email protected]

Çukurova University, Faculty of Science and Letters Department of Chemistry, 01330, Adana

Global warming is the most important problem for humanity all over world because of increasing consumption bases on carbon emission fuels. Renewable energy source as a solar hydrogen generation from water via photoelectrolysis method is a promising option to decrease usage of fossil fuels. Heterogeneous catalysts[1], metal doped[2] and p-n type junction [3] and dye-sensitized catalyst [4] are utilized by the researcher for enhancing photocatalytic activity of the electrode on water splitting. In this study, phosphine complex was synthesized and deposited on ZnO nanorod. The covered with phosphine complex on ZnO nanorod was examined firstly for water splitting via solar radiation to effective hydrogen production by our group in the literature. The photocatalytic activity of electrodes were investigated with I-V measurement at dark and illumination condition. The optic band gap of electrodes were performed with UV-vis spectrometer. The electrode surfaces were characterized FESEM image. Results indicated that the phosphine complex deposited on ZnO nanorod was demonstrated better photocatalytic activity than bare ZnO nanorod solar hydrogen generation from water splitting under solar light.

Key words: Water splitting, Phosphine complex, ZnO nanorod, Hydrogen production,

Figure 1. Schematic of the covered with Cu complex on ZnO nanorod.

References: [1] M. Pori, B. Likozar, M. Marinšek, Z. Crnjak Orel, Fuel Processing Technology, 146 (2016) 39-47. [2] H.D. Dhaygude, S.K. Shinde, N.B. Velhal, M.V. Takale, V.J. Fulari, Materials Research Express, 3 (2016) 086402. [3] A. Dhara, B. Show, A. Baral, S. Chabri, A. Sinha, N.R. Bandyopadhyay, N. Mukherjee, Solar Energy, 136 (2016) 327-332. [4] S.K. Choi, H.S. Yang, J.H. Kim, H. Park, Applied Catalysis B: Environmental, 121-122 (2012) 206-213.

Acknowledgement: The authors would like to acknowledge the funding received from the Scientific and Technological Research Council of Turkey (TUBITAK Project No: 116C035) under the 2236-Co-Funded Brain Circulation Scheme, TUBITAK- BİDEB 2211-National Ph.D. Fellowship Programme, Cukurova University BAP Project No: FDK-2014-3488 and Project No: FBA-2017- 7056.


2 0 1 7 March 20-22


P 3 4

Supramolecular Coordination Complex on the Nanometer Scale With a Ferrocene-Based Phospholane Ligand

Reinhard Hoy and Evamarie Hey-Hawkins


Institute of Inorganic Chemistry, Faculty of Chemistry and Mineralogy, Leipzig University, Johannisallee 29, 04103 Leipzig, Germany

Starting from 1,3,5-tris(p-(diethoxyphosphonylmethyl)phenyl)benzene [1] a straight-forward synthesis of the supramolecular coordination complex shown in Figure 1 was developed. Two of these potentially tetradentate ligands coordinate four AuI atoms in a linear fashion thus forming a cavity with a size of approximately 0.9 x 1.25 nm in which solvent molecules are located. In the solid state, these “molecular boxes” are stacked by π-π interactions [2].

Fig. 1: Supramolecular coordination complex of a ferrocene-based phospholane ligand and

AuI forming a cavity in the nm range. Counterions (chloride) are not shown.

Key words: supramolecular coordination complex References: [1] D. W. Chang, S.-Y. Bae, L. Dai, J.-B. Baek, J. Polym. Sci. Part A: Polym. Chem.

51 (2013) 168–175. [2] C. Janiak, Dalton Trans. 21 (2000) 3885–3896.


2 0 1 7 March 20-22


P 3 5

Aminophosphine-boranes as entry to aminated P-nucleophiles in synthetic chemistry

M. Blum1, Dr. W. Frey1, S. H. Schlindwein1 and D. Gudat1


1University of Stuttgart

Phosphorus nucleophiles made by deprotonation of alkyl- or aryl-phosphines are known for a long time and their use in synthetic chemistry is well established.[1] In contrast, amino-substituted phosphides have barely been described.[2]

Gudat et. al. reported the Umpolung of the P-H bond in diaminophosphines, resulting in a hydridic reactivity of the P-H bond in P-hydrido-1,3,2-diazaphospholenes.[3] Reaction of such a compound with butyllithium led to P-N bond cleavage and destruction of the ring system.[4] However, Knochel et al. demonstrated that borane adducts of acyclic diaminochlorophosphines can be alkylated after treatment with lithium naphthalenide and an alkyl halide.[5] The reaction was postulated to occur via a lithated aminophosphine-borane. Even if direct experimental evidence for these species is still lacking, they are interesting synthons for molecular chemistry.

Here, we present first results of our studies in this area which show that deprotonation of aminophosphine-borane (1) can be established as an alternative access route to P-metalated diaminophosphine-boranes. The products were for the first time characterized by spectroscopic and XRD data and successfully employed in reactions with electrophiles

Key words: Phosphine-borane, Diaminophosphides, Transition metal complexes References: [1] K. Issleib, A. Tzschach , Chemische Berichte, 92(1959), 1118-1126. [2] P. K. Majhi, A. W. Kyri, A. Schmer, G. Schnakenburg, R. Streubel, Chem. Eur. J., 22(2016), 15413-15419. [3] D. Gudat, A. Haghverdi, M. Nieger, Angew. Chem. Int. Ed.,39(2000), No. 17, 3084-3086. [4] A. Haghverdi, Untersuchungen zur Struktur und Reaktivität von Diazaphospholen- Derivaten, Dissertation, 2000.

[5] A. Longeau, P. Knochel, Tetrahedron Letters, 37 (1996), 6099-6102.

P ClN

N

1.2 eq LiBH4, Et2O,0 °C to r.t., 12h

P HN

N

BH3

-LiCl

2.5 M n-BuLi/hexane,Et2O, -78 °C to r.t.,

12h P LiN

N

BH3

-BuH

(1)

P LiN

N

BH3 ZnCl Cl

N N

- LiCl PNN

BH 3

ZnCl

N N


2 0 1 7

March 20-22


P 3 6

From 2H-Phospholes to 1-Phospha-2-azanorbornenes by Phospha-aza-DIELS-ALDER Reactions

Peter Wonneberger1, Evamarie Hey-Hawkins1


1 Institute of Inorganic Chemistry, Faculty of Chemistry and Mineralogy, Leipzig University, Johannisallee 29, 04103 Leipzig, Germany

As formal phosphorus analogous of cyclopentadienes, 2H-phospholes are versatile dienes in phospha-DIELS-ALDER reactions.[1] In the last decades, mainly reactions with 2H-phospholes and carbon dienophiles were reported. In contrast, reports on reactions between 2H-phospholes and heteroatom dienophiles are scarce. One example for such a hetero-DIELS-ALDER reaction with benzaldehydes as dienophiles was published by MATHEY and coworkers.[2] We have now extended this reaction to imines as dienophiles in phospha-aza-DIELS-ALDER reactions.

Differently substituted 2H-phospholes 2 (R1 = Ph) were reacted with an electron-poor imine 3 in a phospha-aza-DIELS-ALDER reaction to give 1-phospha-2-azanorbornenes 4. The 2H-phospholes 2 are obtained in situ as highly reactive intermediates from the corresponding 1H-phospholes by a sigmatropic shift reaction. The reactions are highly regioselective and moderately stereoselective, favouring the endo isomer.

Keywords: 2H-Phospholes, Diels-Alder-reaction, phosphorus-nitrogen-bond References: [1] F. Mathey, Acc. Chem. Res. 2004, 37, 954–960. T. Möller, M. B. Sárosi, E. Hey-Hawkins, Chem. Eur. J. 2012, 18, 16604–16607; T. Möller, P. Wonneberger, M.B. Sárosi, P. Coburger, E. Hey-Hawkins, Dalton Trans. 2016, 45, 1904–1917.

[2] P. Toullec, L. Ricard, F. Mathey, J. Org. Chem. 2003, 68, 2803–2886.

R1P

[1,5-shift]

PR1

1 2

NS

O O

OOEt

3

PN

SO O

R1

OEtO

xylene, 125 −

140 °C PN

SO O

R1

OEtO

endo-4 exo-4

+


2 0 1 7 March 20-22


P 3 7

THE SYNTHESIS AND CHARACTERIZATION OF 2-(di-p-TOLYLPHOSPHINO)BENZALDEHYDE

Burcu Darendeli1, Mustafa Kemal Yılmaz2, Bilgehan Güzel1

e-mail: [email protected] 1 Department of Chemistry, Çukurova University, 01330, Adana, TURKEY

2 Silifke Vocational College, Mersin University, 33343, Mersin, TURKEY

Phosphine based ligands have recently become popular choices as nucleophilic catalysts in organic synthesis [1]. Cause of their strong donor properties they are generally favored to prepare organometallic catalysts [2]. However, to synthesize this type of ligands is very demanding, they will be oxidized very easily. So, to develop air-stable phosphine ligands is a promising research area. For this aim, in this work, a new air-stable phosphine ligand, 2-(di-p-tolylphosphino)benzaldehyde, was synthesized from 2-bromobenzene (Scheme 1). Every single step was identified with 31P and 1H nuclear magnetic resonance (NMR) spectroscopy. The target structure was succesfully synthesized and characterized with NMR, FT-IR and elementel analysis.

Scheme 1. Synthesis of 2-(di-p-tolylphosphino)benzaldehyde

Key words: Phosphine, Ligand, Aryl Bromide, Air-stable

References: [1] METHOT, J.L., ROUSH, W.R., Adv. Synth. Catal., 346 (2004) 1035 – 1050

[2] JENKINS, D.E., ASSEFA, Z., Journal of Molecular Structure, 1133 (2017) 374 – 383

Acknowledgement

This work was supported by the Scientific Research Projects Program (BAP No: FDK-2016-5962), University of Çukurova, Turkey.


2 0 1 7 March 20-22


P 3 8

Electrochemical Properties of Ru(II) Metal Phosphine Complex

Eylül Büşra Hereytani, Fatih Tezcan, Gülfeza Kardaş, Bilgehan Güzel


Chemistry Department, Çukurova Universty, 01330, Adana, TURKEY

The synthesis of metal complexes bearing a phosphine ligand with generally stability and reactivity is still one of essential research topics[1,2]. As the metal-phosphine complexes were coordinated with a second ligand containing the donor group in structure, the electrochemical and photophysical properties can be change[3]. In this study, Ru(II) metal complex of bis(diphenylphosphinemethyl)amino, ((Ph2PCH2)2N(CH2)3(CH3)3) and 4,4’,6,6’-Tetramethyl-[2,2’]bipyrimidine ligands derivative have been synthesized using Schlenk method under nitrogen atmosphere. Metal Complex has been characterized by FT-IR, NMR (1H, 31P) techniques. Electrochemical behaviour of complex has been investigated by cyclic voltammetry. The oxidation and reduction potentials of ruthenium complex were determined utilizing three electrodes configuration at 25°C in 1x10-3 M metal complex at glassy carbon electrode in 0.1 M dichloromethane with solution TBAP as a supporting electrolyte at 100 mV/s scan rate.

Figure 1. Moleculer structures of Ru(II) complexes

Key words: Aminomethylphosphine, bipyrimidine, electrochemical properties

References: [1] Vogler, Arnd, and Horst Kunkely. "Excited state properties of transition metal phosphine complexes." Coordination chemistry reviews 230.1 (2002): 243-251.

[2] Güveli, Şükriye, et al. "Spectroscopic, electrochemical and X-ray diffraction studies on nickel (II)-complexes of acetophenone thiosemicarbazones substituted six-carbon groups." Inorganica Chimica Acta 443 (2016): 7-14.

[3] Sullivan, B. P., D. J. Salmon, and Thomas J. Meyer. "Mixed phosphine 2, 2'-bipyridine complexes of ruthenium." Inorganic Chemistry 17.12 (1978): 3334-3341.

Acknowledgment: The authors are greatly thankful to Unit of The Scientific Research Project Of Çukurova University (Project No: FYL-2015-5201)

NN

R1R1

N N

R1 R1

Ru

P

N

P

Ph Ph

Ph Ph

R2

R2 =

NEt2

R1 =


2 0 1 7 March 20-22


Ring-opening reaction of 2-trifluoromethyl-N-tosylaziridine

with secondary phosphanes as nucleophiles

David Harting,a Takeshi Hanamotob and Jan J. Weiganda*

E-Mail: [email protected]

aTU Dresden, Department of Chemistry and Food Chemistry, 01062 Dresden, Germany bSaga University, Department of Chemistry and Applied Chemistry, Graduate School of Science and

Engineering, Saga 840-8502, Japan

The ring-opening reactions of aziridine 1 with nitrogen and sulfur based nucleophiles

are well established.[1] Contrariwise, the use of phosphanes as nucleophiles is rather

unexplored. In this contribution, we present the reaction of secondary phosphanes R2PH

(R = Ph, tBu, Cy) with 1 to yield bidentate P,N-ligands of type 2.[2] The combination of

a nitrogen and phosphorus in these ligands allows for the complexation of various

transition metals.[3]

Key words: Aziridine, Ring-opening, P,N-ligands References: [1] Y. Takeshiro, K. Hirotaki, C. Takeshita, H. Furuno, T. Hanamoto, Tetrahedron 69 (2013)

7448–7454.

[2] A. Caiazzo, S. Dalili, A. K. Yudin, Org. Lett.4 (2002) 2597–2600.

[3] A. Schnyder, L. Hintermann, A. Togni Angew. Chem. Int. Ed. Engl. 34 (1995) 931–933.

Acknowledgement: We thank the European Research Council (ERC starting grand, SynPhos - 307616)

and the ERASMUS+ program of the TU Dresden and the Saga University for financial support.


2 0 1 7 March 20-22


Synthesis of Azido- and Cyanofluorophosphoranes from

Fluorophosphonium Triflate Salts

Chunxiang Guo, Sivathmeehan Yogendra, Felix Hennersdorf, Jan J. Weigand*


TU Dresden, Department of Chemistry and Food Chemistry, 01062 Dresden, Germany

Fluorophosphonium derivatives exhibit a highly Lewis acidic phosphorus atom[1] and

some possess a remarkable potential in catalytic reactions.[1-3] The synthesis of these derivatives

usually includes the fluorination of an appropriate phosphane with XeF2 and subsequent

fluoride abstraction with for example [Et3Si][B(C6F5)4] [1-4] or Me3SiOTf.[5]

In this contribution we report a convenient and high yielding protocol for the synthesis

of fluorophosphonium cations as triflate salts. Formal F+-transfer towards phosphanes is

achieved with N-fluorobenzenesulfonimide (NFSI) to give NSI salts of the fluorophosphonium

cations (1[NSI]). Subsequent reaction with MeOTf leads to the methylation of the [NSI]-anion

to MeNSI and the fluorophosphonium triflate salts (2[OTf]). The resulting triflate salts are

currently being investigated as catalysts in organic transformation reactions and as precursors

for the preparation of reactive phosphorane derivatives such as 3 and 4.

Key words: Fluorophosphonium cations, phosphorane derivatives.

References: [1] C. B. Caputo, L. J. Hounjet, R. Dobrovetsky, D. W Stephan, Science 341 (2013), 1374 – 1377.

[2] M. H. Holthausen, M. Mehta, D. W. Stephan, Angew. Chem. Int. Ed. 53 (2014), 6538 – 6541.

[3] M. Perez, Z. W. Qu, C. B. Caputo, V. Podgorny, L. J. Hounjet, A. Hansen, R. Dobrovetsky, S.

Grimme, D. W. Stephan, Chem. Eur. J. 21 (2015), 6491 – 6500.

[4] M. Perez, T. Mahdi, L. J. Hounjet, D. W Stephan, Chem. Commun. 51 (2015), 11301 – 11304.

[5] K. Schwedtmann, R. Schoemaker, F. Hennersdorf, A. Bauza, A. Frontera, R. Weiss, J. J Weigand,

Dalton Trans. 45 (2016), 11384 – 11396.

Acknowledgement: The authors thank the ERC (SynPhos 307616) and China Scholarship Council (CSC No. 201506200056)

for financial support.


2 0 1 7 March 20-22


P 4 1

Design of phosphino-naphthyl (P,C) chelate Gold(III) complexes for new reactivities

Feriel Rekhroukh, Abderrahmane Amgoune,* Didier Bourissou*

[email protected]

Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier / CNRS UMR 5069, 118 Route de Narbonne, 31062 Toulouse, France

During the last 15 years gold chemistry experienced an impressive development concerning catalytic applications and gold complexes are no longer considered as chemically inert species. Consequently, an increasing interest was dedicated to the comprehension of fundamental reactivity of gold complexes.1 However, in contrast to the group 10 transition metals, our knowledge of gold chemistry is still limited concerning the elementary steps involved in transition metals catalyzed transformations such as oxidative addition, migratory insertion and β-hydride elimination. In our group, we are investigating the organometallic chemistry and fundamental reactivity of gold complexes.2,3 We recently showed, thanks to rational ligand design, that gold is able to promote the oxidative addition of Csp

2-halide bonds (C-X).4 Migratory insertion and β-H elimination other key organometallic reactions at the basis of important catalytic processes, also remain unknown in gold chemistry. In this context, we recently investigated the coordination-insertion of olefins and the β-hydride elimination reaction with phosphorus containing Au(III)-alkyl complexes (Fig.1).5,6 In this presentation, the straightforward synthesis, the stabilization of Au(III) alkyl complexes supported by phosphine based ligands and their reactivity toward olefins will be discussed. Most significantly experimental and theoretical evidence for the coordination followed by insertion of olefin into Au-C bond but also β-hydride elimination process will be presented.

Fig. 1 : Migratory insertion and β-H elimination processes with (P,C) cyclometalated Au(III) alkyl complex

Key words: Gold chemistry, chelate ligand, phosphine, migratory insertion, β-H elimination.

1. A. S. K. Hashmi, Angew. Chem. Int. Ed. 49 (2010) 5232-5241. 2. M. Joost, P. Gualco, Y. Coppel, K. Miqueu, C. E. Kefalidis, L. Maron, A. Amgoune, D.

Bourissou, Angew. Chem. Int. Ed. 53 (2014) 747-751. 3. J. Guenther, S. Mallet-Ladeira, L. Estevez, K. Miqueu, A. Amgoune, D. Bourissou, J Am Chem

Soc 136 (2014) 1778-1781. 4. M. Joost, A. Zeineddine, L. Estevez, S. Mallet-Ladeira, K. Miqueu, A. Amgoune, D. Bourissou,

J. Am. Chem. Soc. 136 (2014) 14654-14657. 5. F. Rekhroukh, R. Brousses, A. Amgoune, D. Bourissou, Angew. Chem. Int. Ed. 54 (2015) 1266-

1269. 6. F. Rekhroukh, L. Estevez, K. Miqueu, A. Amgoune, D. Bourissou, J. Am. Chem. Soc. 138 (2016)

11920-11929.


2 0 1 7 March 20-22


P 4 2

Ligands for Heterobimetallic Catalysts for Ammonia Synthesis

Wieland Körber1, Evamarie Hey-Hawkins1

e-mail: [email protected] 1 Institute of Inorganic Chemistry, Faculty of Chemistry and Mineralogy, Leipzig University,

Johannisallee 29, 04103 Leipzig, Germany

Ammonia synthesis is among the most important industrial processes and consumes about 1% of the energy produced world-wide. Therefore, understanding and mimicking nature’s way of ammonia generation at ambient conditions is a highly relevant research area.

Recently, ammonia synthesis by homogeneous catalysis has achieved major progress. Currently, two functional catalytic systems are being studied, but both need an improved stability of the catalyst.[1,2] A suitable approach could be to avoid strong acids and metallocenes as sources for protons and electrons, respectively, and use H2 instead. Inspired by the theoretical study of HÖLSCHER et al., the target is a combination of an ammonia-producing catalysts with a hydrogen-cleaving catalysts in one molecule.[3] To this extent we designed a ligand utilizing the boratrane unit of PETERS’ ammonia catalyst and linked it via phenylpyridine to NORTON’s H2-cleavaging catalyst.[1,4] Herein, we present our latest efforts in the synthesis and characterisation of this novel ligand.

B

RPhP PhPFe

N

RPhP

NRhCp*

HH

N

NR =B

PPhRPhP

PPhR

N

Ref. [1]

Ref. [4]

Key words: Ammonia Synthesis, Ligand Design, Heterobimetallic Catalysis References: [1] J. Rittle, J. C. Peters, J. Am. Chem. Soc. 138 (2016) 4243–4248. [2] S. Kuriyama, K. Arashiba, K. Nakajima, Y. Matsuo, H. Tanaka, K. Ishii,

K. Yoshizawa, Y. Nishibayashi, Nat. Commun. 7 (2016) 12181. [3] V. Moha, W. Leitner, M. Hölscher, Chem. Eur. J. 22 (2016) 2624–2628. [4] Y. Hu, J.R. Norton, J. Am. Chem. Soc. 136 (2014) 5938–5948.



2 0 1 7 March 20-22


P 4 3

Phospholium triflates as building blocks for 2D graphene-type materials

Robin Schoemaker, Felix Hennersdorf, Chris Sala and Jan J. Weigand* e-mail: [email protected]

TU Dresden, Department of Chemistry and Food Chemistry, 01062 Dresden, Germany

Phospholes are a well investigated substance class, however only very few examples of diazaphospholium cations are described in literature.[1,2] We developed a facile protocol for the synthesis of cationic, annulated diazaphospholium triflates 1-3[OTf] starting from readily accessible dichlorophosphanyl substituted pyridine derivatives.

NP

N[OTf]

NP

N

[OTf]

NP

N

[OTf]

1[OTf] 2[OTf] 3[OTf] Diazaphospholium cations are feasible building blocks for the bottom-up synthesis of N,P-doped graphene-type materials, a substance class of which interesting electronic properties are expected.[3]

NP

N

[OTf]

3[OTf]

NP

N

[OTf]

4[OTf]

oxidation

3[OTf] is readily oxidized in a Scholl-type reaction to 4[OTf]. Currently, polycyclic phospholium triflates 1-4[OTf] are investigated with respect to their electronical and optical properties. Key words: Phospholes, Heterocycles, Organophosphorus Chemistry, Graphene-Type

Material References: [1] N. Gupta, Top. Heterocycl. Chem. 21 (2010) 175-206. [2] K. Karaghiosoff, C. Cleve, A. Schmidpeter, Phosphorus, Sulfur Relat. Elem. 28 (1986) 289-296. [3] X. Wang, G. Sun, P. Routh, D.-H. Kim, W. Huang, P. Cheng, Chem. Soc. Rev. 43 (2014) 7067-7098.

Acknowledgement: We thank the European Research Council (ERC starting grand, SynPhos - 307616) for financial support.


2 0 1 7 March 20-22


P 4 4

SYNTHESIS OF A NEW CHIRAL HETERO-DENTATE PHOSPHINE LIGAND Burcu Darendeli, Aysen Demir, Bilgehan Güzel


Department of Chemistry, Çukurova University, 01330, Adana, TURKEY

Hetero-dentate ligands with hard and soft P–N donor atoms with interesting properties have been generated and continue to attract interest to date [1]. Upon coordination to transition metals, the hard and soft combination creates higher reactivity [2]. Especially chiral iminophosphine ligands are mostly preferred for organic synthesis. With this type of chiral catalysts, most of industrial intermediates are easily synthesized. For this purpose, in this work, a new chiral iminophosphine ligand was synthesized by condensation of a chiral amine with an aldehyde (Scheme 1). The synthesized product was characterized by 31P and 1H nuclear magnetic resonance (NMR) spectroscopy, FT-IR and elementel analysis.

Scheme 1. Synthesis of iminophoshine ligand

Key words: Imınophosphine, Ligand, Hetero-dentate, Chiral

References: [1] YILMAZ, M.K., GUZEL, B., Applied Organometallic Chemistry, 28 (2014) 529-536

[2] MOTSWAINYANA, W.M., ONANI, M.O., MADIEHE, A.M., SAIBU, M., THOVHOGI, N., LALANCETTE, R.A., Journal of Inorganic Biochemistry, 129 (2013) 112-118

Acknowledgement

This work was supported by the Scientific Research Projects Program (BAP No: FDK-2016-5962), University of Çukurova, Turkey.


2 0 1 7 March 20-22


P 4 5

5-PHOSPHASEMIBULLVALENES: EXPANDING THE SUBSTRATE SCOPE

Daniel Frost, Christian Müller*

e-mail: [email protected], [email protected]

Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstraße 34/36, 14195 Berlin, DE

We recently reported on the photochemical di-π-methane rearrangement of 1-phosphabarrelenes towards 5-phosphasemibullvalenes.[1] This quantitative reaction provides a route to configurationally stable, chiral products, which could be employed as ligands in homogeneous catalysis or in molecular materials. The proposed mechanism for the di-π-methane rearrangement proceeds via the formation of biradical species and was confirmed experimentally and by means of DFT calculations. By changing the substituents on the ligand backbone it is possible to stabilize or destabilize such radicals, driving the reaction to one of the possible products selectively.

We were able to structurally characterize a number of 5-phosphasemibullvalene derivatives, extending the substrate scope of this reaction to the formation of alkyl- and asymmetrically-substituted barrelenes.

The studies on these novel chiral organophosphorus cage compounds lay the foundations for developing a modular synthetic approach to a new class of phosphorus-containing ligands.

Key words: di π-methane rearrangement, heterocycle, chiral ligands, fluorescence, catalysis References: [1] M. Rigo, M. Weber, C. Müller, Chem. Commun. 2016, 7090.

hν PR

Ph

RP

R

Ph

R *

**

*

P P

Se


2 0 1 7 March 20-22


P 4 6

Bisacylphosphines as acac-Type Ligands for Mono- and Bimetallic Complexes

Erik Schrader1, Matthew Baker1, Mark Bispinghoff1,Dr. Hansjörg Grützmacher1 e-mail: [email protected]

1 ETH Zürich, Laboratory of Inorganic Chemistry, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland

Bisacylphosphines have so far been used as precoursors for the synthesis of photoinitiators [1].

Due to their similiarity to the acetylacetone ligand and the possibility of a second coordination through the phosphors atom, bisacylphosphines are excellent candidates for the synthesis of mono- as well as bimetallic complexes.

R

O

P

O

R R

O O

RBAP

-acac

-

Fig 1. Comparison of the bisacylphospine (BAP) and the acetylacetone (acac) system.

By reacting bis(mesitoyl)phoshine with metal halide precoursors in presence of a base, the corresponding BAP-complexes could be isolated, with one example for iron shown below.

A bimetallic complex could be prepared by reacting the aluminium complex of bis(mesitoyl)phosphine with AuCl(SMe2).

Fig 2. Structures of [Fe(P(COMes)2)2)(THF)2] (left) and [Al(P(COMes)2)3)(AuCl)3)] (right)

Key words: Phosphine Ligands, Bimetallic Complexes References: [1] Huber, A. et al, Angew. Chemie Int. Ed., 2012, 51, 4648.


2 0 1 7 March 20-22


P 4 7

NEW TRIARYILTELLURONIUM SALTS OF ORGANOPHOSPHORUS LIGANDS

Eleonora Denes and Anca Silvestru


Babeș-Bolyai University, Department of Chemistry, Center of Supramolecular Organic and Organometallic Chemistry, 11 Arany János Street, 400028, Cluj-Napoca,

Romania)

Organotellurium compounds attracted a considerable increased interest in recent years due mainly to their potential applications as precursors for nanomaterials.[1] The triorganotellurium(IV) compounds, either halides and pseudohalides or species containing chelating ligands, were described as triorganotelluronium salts which behave as 1 : 1 electrolytes, at least in polar solvents.[2]

We report here about several ionic compounds containing the hypervalent cation [{2-(Me2NCH2)C6H4}3Te]+ and anionic organophosphorus ligands of type [(R2PX)(R'SO2)N]- (R = Ph or OEt; R' = alkyl, aryl; X = S, O) and, respectively [(R2PX)(R'2PY)N]- (R, R' = Ph, Me, OEt; X, Y = O, S, Se).

The new compounds were structurally characterized in solution by multinuclear NMR (1H, 13C, 31P and 125Te). For several of them the solid state structure was determined by single-crystal X-ray diffraction. Key words: triorganotellurium(IV) compounds, organophosphorus ligands, NMR spectroscopy, crystal and molecular structure. References: [1] T. Chivers, R. S. Laitinen, Chem. Soc. Rev. 44 (2015) 1725–1739. [2] J. D. Woollins, R. S. Laitinen (eds.), Frontiers of Selenium and Tellurium Chemistry: From Small Molecules to Biomolecules and Materials’, Springer-Verlag, Heidelberg, 2011.


2 0 1 7 March 20-22


P 4 8

GROUP 12 METAL COMPLEXES WITH HYPERVALENT TRIARYLPHOSPHANES

Răzvan Șuteu and Anca Silvestru


Babeș-Bolyai University, Department of Chemistry, Center of Supramolecular Organic and Organometallic Chemistry, 11 Arany Janos Street, 400028, Cluj-Napoca, Romania

Triarylphosphanes are well-known as stabilizing ligands for late d metals. Group 10 (Pd, Pt) and 11 (Au, Ag) complexes are largely used as catalysts in different organic transformations, while group 12 derivatives found applications as precursors for nanomaterials.

During the last years our interest was focused on triarylphosphanes bearing organic groups with pendant arms capable for intramolecular coordination, respectively compounds of type [2-(R2NCH2)C6H4]xPh3-xP (R = Me, Et; x = 1 – 3), which favour the formation of monomeric metal complexes with increased hydrolytic and thermal stability.[1,2]

Here we report about several group 12 (Zn, Cd, Hg) metal complexes with such triarylphosphanes. Their solution behavior was investigated by multinuclear NMR spectroscopy (1H, 13C, 31P, 113Cd, 199Hg, as appropriate). The solid state structures determined by single-crystal X-ray diffraction revealed the formation of hypervalent species stabilized by intramolecular N→M coordination.

Key words: hypervalent triarylphosphanes; group 12 metal complexes; multinuclear NMR;

single-crystal X-ray diffraction. References: [1] A. Covaci, R. Mitea, I. Hosu, A. Silvestru, Polyhedron, 72 (2014) 157-163.

[2] R. Mitea, A. Covaci, C. Silvestru, A. Silvestru, Rev. Roum. Chim., 58 (2013) 265-273.


2 0 1 7 March 20-22


P 4 9

TOWARDS NEW GERMAPHOSPHAALKENYL DERIVATIVES

Lavinia Buta, Ionuţ-Tudor Moraru, Gabriela Nemeş e-mail: [email protected]; [email protected]

Babeş-Bolyai University, Faculty of Chemistry and Chemical Engineering, 11 Arany János, RO-400028, Cluj-Napoca, Romania.

Abstract. A new germaphosphaalkenyl derivative containing the –P=C–Ge< moiety was successfully synthesized following the synthetic routes described in the literature1-3. The compound 1 (Figure 1) was completely characterized by NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction methods. These types of systems were stabilized using adequate substituents on both phosphorus and germanium atoms; in this case the germanium atom was stabilised by insertion in a fluorenyl type fragment. DFT calculations and NBO analysis were performed in order to gain a more detailed insight on the chemical bonding and on the structural features of the analyzed compounds. Both experimental and theoretical methods show a successful selection of the precursors in order to obtain the desired compounds with the P=C–E unit, where E is a heavy element of the 14 group.

Ge C P

Cl

Cl

1 Figure 1.

Keywords: phosphaalkenes, low coordinated compounds, dihalogenated derivatives

References: [1] B. E. Eichler, D. R. Powell, R. West, Organometallics, 17 (1998) 2147-2148. [2] J. Escudié, H. Ranaivonjatovo, M. Bouslikhane, Y. El Harrouch, L. Baiget, G. Cretiu Nemes, Russ. Chem. Bull., 53 (2004) 1020-1033. [3] N. Tokitoh, K. Kishikawa, R. Okazaki, Chem. Lett., 8 (1998 ) 811-812.




2 0 1 7 March 20-22


P 5 0

TRICYCLIC DITHIOLE-2-THIONE-BASED 1,4-DIHYDRO-1,4-DIPHOSPHININES: A DIFUNCTIONAL BUILDING BLOCK FOR POLYMERS?

Alexander Gese, Rainer Streubel*


Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn, Gerhard Domagk-Str.1, 53121 Bonn, Germany

It is well known for a long time that tetrathiafulvalene (TTF) forms charge transfer complexes with easily reducible organic compounds, e.g., tetracyanoquinodimethane (TCNQ), showing high electrical conductivity over a wide temperature range.[1] Due to this phenomenon they are often called “organic metals”. It is also well established that dithiole-2-thiones and their derivatives provide access to functionalized tetrathiafulvalenes via different C,C-coupling reactions.[2]

Herein, it is shown that backbone P-functionalized dithiole-2-thiones 1 can be coupled using triethylphosphite to furnish the TTF derivative 2 (Scheme 1); E,Z-isomers are observed in case of mono(diphenylphosphanyl)dithiole-2-thiones. To exploit this methodology trans-ferability to annulated bis-dithione derivatives possessing a pseudo-linear array is desirable.

2 P(OEt)3, 105 °C

TolueneS

SS

Ph2P

Ph2P

S

S

Ph2P

Ph2P

S

S PPh2

PPh2

1/2

1 2 Scheme 1: Coupling reaction of phosphorus functionalized dithiole-2-thiones 1 to the corresponding

TTF derivative 2.

Therefore, a protocol was designed to synthesize the first tricyclic 1,4-dihydro-1,4-diphosphinine 5 (Fig. 1) with two P-bridged dithiole-2-thione units, which will be reported.[3]

P

P

S

SS

SSS

NEt2

Et2N5

Figure 1: Tricyclic 1,4-dihydro-1,4-diphosphinine 5 based on 1,3-dithiole-2-thiones.

Furthermore, first studies on the reactivity of the 1,4-dihydro-1,4-diphosphinine 5 will be presented including P-derivatisations as well as S-methylation and reduction reactions.

Keywords: Tetrathiafulvalene, 1,4-dihydro-1,4-diphosphinines

References: [1] J. Ferraris, D. O. Cowan, V. V. Walatka, J. H. Perlstein, J. Am. Chem. Soc. 95 (1973) 948-949.

[2] a) J. M. Fabre, Chem. Rev. 104 (2004) 5133-5150; b) M. Narita, C. U. Pittman Jr., Synthesis 8 (1976) 489-514.

[3] A. Gese, M. Akter, G. Schnakenburg, R. Streubel, to be published.



2 0 1 7 March 20-22


P 5 1

OPTICAL AND ELECTROCHEMICAL PROPERTIES OF A NOVEL DYE- SENSITIZED Pd(II) COMPLEX

Gurbet YERLIKAYA1, Gulfeza KARDAS1 e-mail:[email protected]

1Çukurova University, Faculty of Science, Department of Chemistry, 01330, Adana, Turkey

Transition metal complexes are of great significance owing to their uniquely properties, nonlinear optics and luminescence[1]. Therefore, there has been an increasing interest in this field and enormous progress has been made in recent times[2] In this study, Pd(II) metal complex of bis(diphenylphosphinemethyl)amino ligands, ((Ph2PCH2)2N(CH2)3(CH3)3), has been synthesized using Schlenk method under nitrogen atmosphere. Finally, the metal phosphine complex has been reacted with 2,2′-Bipyridyl to give heteroleptic Pd(II) metal complexes at room temperature. The structure of metal complex has been characterized by FT-IR, NMR (1H, 31P). Electrochemical behavior of complexes has been investigated by cyclic voltammetry. The oxidation and reduction potentials of palladium complex were determined with three electrodes configuration at 25°C in 1x10-3M metal complexes at glassy carbon electrode in 0.1 M dichloromethane with solution TBAP as a supporting electrolyte. Emission spectra was taken using 1x10-3M solution of dichloromethane.

E (V) (Ag/AgCl)-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2

i (m

A)

-6e-5

-5e-5

-4e-5

-3e-5

-2e-5

-1e-5

0

1e-5

λ/nm

500 510 520 530 540 550 560

Emis

sion

Inte

nsity

(a.u

)

0

2

4

6

8

10

12

14

16

18

λem= 528 nm

E (eV)2,79 2,80 2,81 2,82 2,83

(αhυ

)2 / (e

V cm

-1 )2

0,020

0,022

0,024

0,026

0,028

0,030

0,032

Eg=2.7945

Figure 1. a) Cyclic voltammetry behavior of 1x10-3M heteroleptic Pd(II) metal complex. b) Emission spectrum of heteroleptic Pd(II) metal complex in dichloromethane c) Optical band gap of heteroleptic Pd(II) metal complex.

Key words: Emission, Cyclic Voltammetry, Synthesis

References: [1] B.J. Coe, S.P. Foxon, E.C. Harper, M. Helliwell, J. Raftery, C.A. Swanson, B.S. Brunschwig, K. Clays, E. Franz, J. Garin, J.s. Orduna, P.N. Horton, M.B. Hursthouse, Journal of the American Chemical Society 132, 1706–1723(2010). [2] N.J. Long, C.K. Williams, Angewandte Chemie International Edition 42, 2586–2617(2003). Acknowledgement:The authors are greatly thankful to Unit of The Scientific Research Project Of Çukurova University (BAP) for financial support (Project Number: FDK-2014-3517)

a) b) c)


2 0 1 7 March 20-22


P 5 2

Potassium-2,3,4,5-tetraadamantyl-cyclopentaphosphanide – Synthesis and Properties

Toni Grell, Evamarie Hey-Hawkins e-mail: [email protected]

Institute of Inorganic Chemistry, Faculty of Chemistry and Mineralogy, Leipzig University, Johannisallee 29, 04103 Leipzig, Germany

Phosphorus-rich metal phosphides (MxPy, y > x) play an important role in materials science.[1] They can possess interesting properties such as superconductivity or catalytic activity and can be used as corrosion inhibitors and capacitors. However, the preparation of these compounds is challenging, as they tend to decompose at elevated temperatures to give white phosphorus (P4) and metal-rich phosphides. As a consequence, high-temperature and related syntheses cannot be considered for their preparation.

P

PP

P

P

1Ad

1Ad

1Ad

1Ad

C

C'A

B'

B 1Ad =

K

The aim of this work is to overcome this problem by employing the mild decomposition of oligophosphanide complexes.[2,3] This is supposed to be achieved by preparing complexes of oligophosphanides and converting them to metal phosphides by subsequent thermal treatment. This work shows the synthesis and properties of a novel oligophosphanide. Furthermore, the coordination behaviour of this compound is discussed.

Keywords: Oligophosphanides

References: [1] H.-G. von Schnering, W. Hönle, Chem. Rev. 88 (1988) 243–273.

[2] S. Gómez-Ruiz, E. Hey-Hawkins, Coord. Chem. Rev. 255 (2011) 1360–1386.

[3] A. Kircali, P. Lönnecke, E. Hey-Hawkins, Z. Anorg. Allg. Chem. 640 (2014) 271–274.


2 0 1 7 March 20-22


P 5 3

Separation of Na3VO4 and Na2CrO4 at basic pH by solvent extraction

Man Feng1,2,3, Felix Hennersdorf3, Marco Wenzel3, Hao Du1,2, Shaona Wang1, Shili Zheng1, Yi Zhang1, Jan J. Weigand*,2

E-mail:[email protected] 1National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Key

Laboratory of Green Process and Engineering, Institute of Process Engineering,Chinese Academy of Sciences, 100190 Beijing, China

2University of Chinese Academy of Sciences, 100049Beijing, China 3TU Dresden, Department of Chemistry and Food Chemistry, 01062 Dresden, Germany

Novel vanadium slag treatment process focuses on the design of integrated recovery of vanadium and associated chromium simultaneously by using Sub-Molten Salt (SMS) method.[1] Based on our investigation of the solubility data, separation of Na3VO4 and Na2CrO4 from the obtained alkaline leaching solution by crystallization was possible.[2-3]

However, the obtained crystallized material still contains 3.2% Na2CrO4 impurity.

In this contribution, we report optimized crystallization processes that enable the isolation of sodium vanadate with a sodium chromate impurity of 0.7%, only. Detailed analysis of the obtained material employing Karl-Fischer titrations and single crystal X-ray diffraction reveal the formation of Na3VO4·7H2O. In addition, the results of solvent extraction studies for a further purification of Na3VO4 employing quaternary amine Aliquat 336 and mixtures of Aliquat 336 and solvating extractants, such as Tri-n-butyl phosphate (TBP) are discussed.

Key words:Na3VO4; Na2CrO4;Separation; Crystallization; Extraction References: [1] Sh. L. Zheng, H. Du, Sh. N. Wang, X. H. Wang, Y. Zhang, Chinese Patent, CN102127655A [2] M. Feng, Sh. L. Zheng,H. Du, Sh. N. Wang, Y. Zhang, Fluid Phase Equlib.360(2013) 338-342. [3] M. Feng, Sh. N. Wang, H. Du,Sh. L. Zheng,Y. Zhang, 6th International Conference of Hydrometallurgy, Beijing, 2014.

Acknowledgement: The authors gratefully thank the financial support from the Major State Basic Research Development Program of China (973 program, No. 2013CB632605), Science and Technology ServiceNetwork Initiative of Chinese Academy of Sciences (No.KFJ-SW-STS-148), National Natural Science Foundation of China (No. 51274178 and 51274179), the China Scholarship Council (CSC No. 21504910560), the ERC (ERC starting grant SynPhos: 307616) and the Fonds der ChemischenIndustrie (FCI, Kekulé scholarship for F. H.).


2 0 1 7 March 20-22


P 5 4

Phenylene-bridged frustrated Lewis pair chemistry

Flip Holtrop, Daniel Hendriks, J. Chris Slootweg* e-mail: [email protected]

Frustrated Lewis pairs (FLPs) combine a Lewis acidic and Lewis basic site granting access to interesting chemistry. For example, FLPs are able to heterolytically cleave dihydrogen allowing for their use as organocatalysts in hydrogenation reactions.[1] In addition, FLPs can activate a variety of small molecules illustrating their potential for further organocatalytic applications. Furthermore, FLPs can be used as ambiphilic ligands which exhibit interesting coordination chemistry. The combination of donating and accepting ligands is relatively unexplored, however, recent development demonstrates their ability to facilitate activation of a variety of bonds (H-H, Si-H, C-H).[2]

This work shows the synthesis of novel o-phenylene-bridged phosphine boranes. Application of these FLPs as organocatalysts for dehydrogenation as well as their ambiphilic ligand properties are being researched.

Br

Br

PPh2

Br

PPh2

BR2

1. nBuLi2. Ph2PCl

1. nBuLi2. R2BCl

-110°C

Key words: Frustrated Lewis pairs, chloroboranes, synthesis References: [1] D. Stephan, G. Erker, 54, (2015) 6400 Angew. Chem. Int. Ed. [2] M. Devillard, G. Bouhadir, D. Bourrissou, 54 (2015) 730 Angew. Chem. Int. Ed.


2 0 1 7 March 20-22


P 5 5

Dynamic resolution of P-heterocyclic phosphine oxides via covalent diastereomeric intermediates

R. Herbay, P. Bagi, E. Fogassy, G. Keglevich


Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, Budapest, Hungary

Optically active phosphines form an important group among organophosphorus compounds, as their transition metal complexes are widely used catalysts in homogeneous enantioselective catalytic reactions.1,2 Which fact also underlies the synthetic value of optically active protected phosphines (e.g. phosphine-boranes or phosphine-oxides).

Continuing the work of our research group in the field of P-heterocyclic compounds,3 we aimed at the dynamic resolution of optically active phospholene oxides (1*) via covalent diastereomeric intermediates using the methods found in the literature.4,5

First, aryl- or alkyl-3-phospholene oxides (1) were reacted with oxalyl chloride to give the corresponding chlorophosphonium salts (2). The cyclic chlorophosphonium salts (2) were reacted with chiral alcohols (R*OH) to afford diastereomeric alkoxyphosphonium salts (4) in a ratio different from 1:1. Optically active 3-phospholene oxides (1*) were formed by the Arbuzov-collapse of the diastereomerically enriched alkoxyphosphonium salts (4).

PO Y

(COCl)2solvent

0°C

PCl Y

+

Cl-

-78°C

solventR*OH

PR*O Y

+

Cl-

60°Csolvent P

O Y

Y = aryl,

alkyl

1 2 3 1*

Key words: phospholene oxides, dynamic resolution, chlorophosphonium salts, alkoxyphosphonium salts

References: [1] Börner, A., Ed. Phosphorus Ligands in Asymmetric Catalysis; Wiley-VCH: Weinheim, 2008. [2] Kollár, L.; Keglevich, G. Chem. Rev. 2010, 110, 4257.

[3] Bagi, P.; Ujj, V.; Czugler, M.; Fogassy, E.; Keglevich, G. Dalton Trans. 2016, 45, 1823.

[4] Rajendran, K. V.; Nikitin, K. V.; Gilheany, D. G. J. Am. Chem. Soc. 2015, 137, 9375.

[5] Nikitin, K.; Rajendran, K. V; Müller-Bunz, H.; Gilheany, D. G. Angew. Chemie - Int. Ed. 2014, 53, 1906.


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P 5 6

SYNTHESIS OF CO2 SOLUBLE PHOSPHINOETHANE LIGANTS AND THEIR

RHODIUM(I) COMPLEXES FOR USING AS HYDROGENATION CATALYST

Mustafa Kemal Yılmaz1, Özge Kırdar2 and B. Güzel 2

1Mersin University Vocational School of Silifke, TURKEY 2Çukurova University Sci. and Lett. Fac. Chemistry Department, 01330, Adana, TURKEY

Derivatives of phosphine ligands and their rhodium complexes have found important applications as catalysts with high yields. In the last two decades there has been increasing interest in using supercritical carbon dioxide (scCO2) as the reaction medium for organic synthesis, because of the toxic effect of organic solvents[1,2]. It is well known that fluorine groups attached to ligands increase their solubility in scCO2 [3]. In this study, fluorous derivatives of 1,2-bis(diphenylphosphino) ethane (Xn) containing 3,5-bis(trifluoromethyl)phenyl and meta-(1H,1H,2H,2H-perfluoroalkyl)phenyl functions were used in the synthesis of fluorous derivatives of [Rh(COD)Xn]BArF (n:1= 3,5-(CF3)2C6H3, n:2 = m-(1H,1H,2H,2H-perfluoroalkyl)phenyl), and characterized by using spectroscopic methods such as FT-IR, 1H, 19F and 31P NMR. Solubility studies in sc CO2 were performed at the conditions of 343oK, 2300 psi pressure. The synthesized catalyst shows high coversion on styrene hydrogenation reaction.

[Rh(COD)Xn]BArF:

CH

CHPR2

PR2

H3C

H3C

+ [(COD)2Rh]+BArF-CH

CHH3C

H3C

P

P

RR

RR

Rh BArF-

+

BArF: Tetrakis(bis 3,5-ditrifluoromethyl phenyl)borat

R------ Xn : (n:1) = 3,5-(CF3)2C6H3 (n:2) = m-(1H,1H,2H,2H-perfluoroalkyl)phenyl

Key words: Phosphine, Supercritical Fluids, Fluorinated ligand, Hydrogenation [1] S. Haji, and C. Erkey, Tetrahedron. 2002, 58, 3929 - 3941. [2] G. Francio, W. Leitner, Journal of Organometallic Chem. 2001, 621, 130 - 142. [3] B. Güzel, M.A. Omary, J.P. Fackler, A. Akgerman, Inorg. Chem. Acta. 2001, 325, 45 - 50.


2 0 1 7 March 20-22


P 5 7

GOLD(I)/(III) COORDINATION COMPOUNDS WITH PHOSPANE AND POLYFLUORINATED ARYL LIGANDS

Alexandru Sava, Bernadette Dan, Cristian Silvestru and Ciprian I. Raț


Centre of Supramolecular Organic and Organometallic Chemistry, Department of Chemistry, Faculty of Chemistry and Chemical Engineering, Babeş-Bolyai University

11 Arany Janos, 400028 Cluj-Napoca, Romania

Although phosphane-gold coordination chemistry is very rich, only a few examples containing ligands with a m-terphenyl backbone are known.1-2 Also, phosphane-gold complexes with highly electron-deficient polyfluorinated aromatic ligands have found various applications such as boron transmetalation,3 arene cross-coupling under neutral conditions,4-5 or phosphonium formation by reductive elimination from gold(III) complexes.6

We report here the synthesis and characterization of four novel gold complexes with bulky polyfluorinated ligands: 2,4,6-(C6F5)3C6H2Au(PPh3) (1), 2,6-(C6F5)2C6F3Au(PPh3) (2), [2,4,6-(C6F5)3C6H2Au]2(dppe) [dppe = 1,2-(Ph2P)2C2H4] (3) and 2,4,6-(C6F5)3C6H2AuCl2(PPh3) (4). Gold(I) compounds were prepared by reacting 2,4,6-(C6F5)C6H2Li or 2,6-(C6F5)2C6F3Li with the corresponding phosphanegold(I) chloride, while 4 was obtained by oxidation of 1 with PhICl2. Compounds 1-4 were characterized by multinuclear NMR spectroscopy and mass spectrometry. The molecular structures of 1, 2 and 4 were determined by single crystal X-ray diffraction.

Molecular structure of 4. Hydrogen atoms were omitted for clarity.

Key words: phosphane, gold, polyfluorinated aryl, m-terphenyl References: [1] G. W. Rabe, N. W. Mitzel, Inorg. Chim. Acta 316 (2001) 132-134. [2] M. Stollenz, D. Taher, N. Bhuvanesh, J. H. Reibenspies, Z. Baranova, J. A. Gladysz, Chem. Commun. 51 (2015) 16053-16056. [3] M. Hofer, E. Gomez-Bengoa, C. Nevado, Organometallics 33 (2014) 1328-1332. [4] M. Hofer, C. Nevado, Tetrahedron 69 (2013) 5751-5757. [5] M. Hofer, A. Genoux, R. Kumar, C. Nevado, Angew. Chem., Int. Ed. 55 (2016) 1-6. [6] H. Kawai, W. J. Wolf, A. G. DiPasquale, M. S. Winston, F. D. Toste, J. Am. Chem. Soc. 138 (2016) 587-593.


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P 5 8

New Halogenated Diphosphane Dichalcogenides

D. Upmann1 and P. G. Jones1 e-mail: [email protected]

1Institute of Inorganic and Analytical Chemistry, TU Braunschweig, Hagenring 30, 38106 Braunschweig, Germany

Phosphane chalcogenides are known to be good donors towards elemental bromine and iodine. Numerous reports of such adducts can be found in the literature. These products feature different forms such as T-shaped or linear geometry and may be either covalent or ionic.[1] For the adducts of diphosphane diselenides dppmSe2 and dppeSe2 with elemental bromine and iodine, structures were proposed, but never confirmed by X-ray crystallography (Figure 1).[2] We now have halogenated phosphane chalcogenides with alkyl groups at the phosphorus atom, and have also obtained single crystals of the dppmSe2 and dppeSe2 adducts.

PhP

Se Ph

(CH2)nP

Ph

Ph

SeBr

Br

Br

Br

PhP

Se Ph

(CH2)n

PPh

Ph

SeI

II

I Figure 1: Proposed structure of dppmSe2 (n = 1) and dppeSe2 (n = 2) adducts with bromine

and iodine.

Reaction of dppmSe2 and dppeSe2 with iodine revealed the formation of two different products. With dppeSe2, the proposed product with a nearly linear Se–I–I unit is formed, whereas dppmSe2 forms a [dppmSe2–I]+ heterocycle. Such a heterocycle is also obtained in the reaction of diprpmSe2 with iodine. X-ray structures of the bromination derivatives of dppmSe2 and dppeSe2 confirmed the proposed products. Excess bromine led to decomposition of the phosphane selenides and the formation of a dppeBr2

2+ or diprpmBr22+ cation.

After the difficult synthesis of the ethylene-bridged diphosphane diprpe, we can now also report the halogenation products of diprpeSe2.

Key words: Diphosphane Dichalcogenides, Halogenation, Adducts References: [1] (a) C. G. Hrib, F. Ruthe, E. Seppälä, M. Bätcher, C. Druckenbrodt, C. Wismach, P. G. Jones, W. W. du Mont, V. Lippolis, F. A. Devillanova, M. Bühl, Eur. J. Inorg. Chem., 2006, 88. (b) W. W. du Mont, M. Bätcher, C. Daniliuc, F. A. Devillanova, C. Druckenbrodt, J. Jeske, P. G. Jones, V. Lipolis, F. Ruthe, E. Seppälä, Eur. J. Inorg. Chem., 2008, 4562. (c) J. S. Ritch, T. Chivers, D. J. Eisler, H. M. Tuononen, Chem. Eur. J., 2007, 4643.

[2] C. G. Hrib, P. G. Jones, W. W. du Mont, V. Lippolis, F. A. Devillanova, Eur. J. Inorg. Chem., 2006, 1294.


2 0 1 7 March 20-22


P 5 9

Synthesis, Structure and Properties of the Strong Brønsted Acid Catalyst, Bis(difluoromethlene)-1,1’-binaphthyl phosphinic acid.

Jay A. Dixon, Andrew J. M. Caffyn*


Div. of Chemistry & Env., Manchester Metropolitan University, U.K.

Chiral phosphorus based Brønsted acids synthesised from 1,1’-binaphthol (BINOL) have attracted much interest in recent years. The desirability of more acidic chiral BINOL-derived acids, for the activation of challenging substrates has been noted.1,2 Bis(difluoromethylene)-1,1’-binaphthyl phosphinic acid has been synthesised from BINOL and screened as a Nazarov cyclisation catalyst. Tests indicate that bis(difluoromethylene)-1,1’-binaphthyl phosphinic acid is a significantly stronger acid than related BINOL-based analogues.

Key words: Phosphinic, Brønsted, Catalyst References: [1] K. Kaupmees, N.Tolstoluzhsky, S. Raja, M. Rueping, I. Leito, Angew. Chem. Int. Ed. 52, (2013) 11569-11572.

[2] T. Akiyama, Chem. Rev. 107, (2007) 5744-5758.


2 0 1 7 March 20-22


P 6 0

Controlling the 3D arrangement of phosphaphenalenes in the solid state

Carlos Romero-Nieto,1 Philip Hindenberg,1 e-mail: [email protected]

1Institute of Organic Chemistry, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg

The unceasing demand for smaller, more energy-efficient electronic devices has resulted in an exponential development of new and improved materials. In this context, the incorporation of phosphorus units into organic π-conjugated compounds has enabled the development of materials with novel and unique properties.1 Particularly, the unusual electronic features of phosphorus- based π-extended architectures offer a wide variety of synthetically facile possibilities that can be undertaken to modify the electronic and luminescent properties of the product materials.1 Despite the unique properties of the latter and due to the infancy of this research field, extensive investigations not only focused on synthesizing new phosphorus-based systems but also on their implementation into functional devices are still nowadays required to reveal the full potential of such novel materials. One of the most important parameters that determines the performances of optoelectonic devices is the 3D arrangement of the molecules in the solid state.

Fig. 1. Phosphaphenalene

In this communication, I will present the synthesis and properties of novel phosphaphenalene derivatives (Figure 1).2 Morevoer, I will show our advances in the development of new strategies to keep control over the 3D arrangement of fused six-membered phosphorus heterocycles in the solid state. I will furthermore introduce our efforts to establish robust structure-properties relationships.

Key words: Phosphaphenalenes, 3D arrangement, optoelectronic properties.

References: [1] a) T. Baumgartner, Acc. Chem. Res., 47, (2014), 1613. b) Baumgartner T.; Reau R. Chem. Rev. 106, (2006), 4681. [2] C. Romero-Nieto, A. López-Andarias, C. Egler-Lucas, F. Gebert, J.-P. Neus, O. Pilgram, Angew. Chem. Int. Ed. 54, (2015), 15872.


2 0 1 7 March 20-22


P 6 1

NOVEL PREPARATION AND APPLICATION OF P-CHIRAL PHOSPHINE OXIDES

Péter Bagi, Réka Herbay, Bence Varga, Petra Nagy, Kinga Juhász, Elemér Fogassy, György

Keglevich [email protected]

Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, Budapest, Hungary

Optically active organophosphorus compounds, especially the ones bearing P-stereogenic center(s) are of great importance in organic syntheses. An important application is the use of chiral P-ligands in transition metal catalysts [1]. Moreover, these compounds can also be organocatalysts in their own right [2]. However, there are a few methods available for the preparation of P-chiral compounds which is still a limiting factor for their widespread application [3].

Our research group found, that TADDOL derivatives and Ca2+ salts of the dibenzoyl- and di-p-toluoyl-tartaric acid seem to be generally applicable resolving agents for enantiomeric separation of P-stereogenic organophosphorus compounds including cyclic and acyclic secondary and tertiary phosphine oxides or phosphinates [4].

A few synthetic applications of the cyclic and acyclic P-chiral compounds were also demonstrated. The platinum-complexes incorporating optically active P-heterocyclic ligands were used as catalysts in the hydroformylation of styrene [5]. Cyclic and acyclic P-stereogenic phosphine oxides were applicable pre-catalysts in enantioselective catalytic Wittig-reactions.

PR1 R2

R3O

R = H, alkyl, aryl

PR1 R3

R2

OP

R1 R3R2

Oresolution +

Key words: P-stereogenic, phosphine-oxides, optical resolution, P-ligand References: [1] A. Börner ed., Phosphorus Ligands in Asymmetric Catalysis, Wiley-VCH, Weinheim, 2008. [2] M. Benaglia, S. Rossi, Org. Biomol. Chem. 8 (2010), 3824-3830. [3] A. Grabulosa, P-Stereogenic Ligands in Enantioselective Catalysis, The Royal Society of Chemistry, Cambridge, 2010. [4] P. Bagi, V. Ujj, M. Czugler, E. Fogassy, G. Keglevich, Dalton Trans. 45 (2016) 1823-1842. [5] P. Bagi, T. Kovács, T. Szilvási, P. Pongrácz, L. Kollár, L. Drahos, E. Fogassy, G. Keglevich, J. Organomet. Chem. 751 (2014) 306-313.


2 0 1 7 March 20-22


P 6 2

Hydrothermal Syntheses and Characterization of the Metal-Organic Frameworks Containing Lanthanides and Organophosphonate Ligands

Burak Ay, Emel Yildiz,


Cukurova University Arts & Science Faculty Dept.of Chemistry 01330 Adana/TURKEY

Metal-organic frameworks (MOFs), also called porous coordination polymers or porous coordination networks, have emerged as a special class of nanoporous materials.

In this project, novel multiple organophosphonate ligands and their lanthanides complexes were synthesized as MOFs under hydrothermal conditions. Their luminescence properties will be investigated. The syntheses can be examined in two sections; a) Syntheses of the organophosphonate ligands: Organophosphonate ligands are synthesized using mono, di and tri aromatic ligands. b) Syntheses of the MOFs: Synthesized organophosphonate ligands and their Ce3+, Pr3+ metal complexes are synthesized under the hydrothermal conditions.

Key words: Hydrothermal Synthesis, Organophosphonate, MOFs, Lanthanides References: [1] De Burgomaster, P., Darling, K., Jones, S., Zubieta, J., 2010. Inorganica Chimica Acta, 364, 150-156.

[2] S. Bauer, T. Bein, N.Stock, 2006. Journal of Solid State Chemistry, 179, 145-155.


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2 0 1 7 March 20-22


LIST OF PARTICIPANTS


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March 20-22

List of Participants Ms. Acar Ilay Ceren Yildiz Technical University Istanbul-Turkey [email protected] Ms. Aysen Demir Çukurova University Adana-Sericam- Turkey [email protected] Dr. Bagi Péter Budapest University of Technology and Economics Budapest- Hungary [email protected] Mr. Balázs Gábor University of Regensburg Regensburg-Germany [email protected] Ms. Begum Imtiaz University of Bonn Bonn- Germany [email protected] Mr. Beil Andreas ETH Zurich Zurich-Switzerland [email protected] Dr. Benkő Zoltán Budapest University of Technology and Economics Budapest- Hungary [email protected] Mr. Bispinghoff Mark ETH Zurich Zurich-Switzerland [email protected] Mr. Blum Markus University of Stuttgart Stuttgart-Germany [email protected]

Mr. Bockfeld Dirk TU Braunschweig Braunschweig-Gemany [email protected] Dr. Bodensteiner Michael University of Regensburg Regensburg-Germany [email protected] Mr. Boom Devin Vrije University of Amsterdam Amsterdam-Netherlands [email protected] Mr. Botez Laurian University of Amsterdam Amsterdam- Netherlands [email protected] Dr. Bresien Jonas University of Rostock Rostock- Germany [email protected] Ms. Buta Lavinia Babes-Bolyai University Cluj-Napoca- Romania [email protected] Mr. Buzsáki Dániel Budapest University of Technology and Economics Budapest- Hungary [email protected] Dr. Caffyn Andrew Manchester Metropolitan University Manchester-UK [email protected] Prof. Caminade Anne-Marie LCC-CNRS Toulouse- France [email protected]


March 20-22

Dr. Caporali Maria CNR ICCOM Florence- Italy [email protected] Ms. Chadwick Ailis University of Bristol Bristol- UK [email protected] Mr. Chunxiang Guo TU Dresden Dresden- Germany [email protected] Assoc. Prof. Cristea Castelia Babes-Bolyai University Cluj-Napoca- Romania [email protected] Mr. D´Imperio Nicolas Uppsala University Uppsala- Sweden [email protected] Ms. Darendeli Burcu Çukurova University Adana-Sericam- Turkey [email protected] Dr. de Boer Marissa University of Amsterdam Amsterdam- Netherlands [email protected] Ms. De Jong Bas University of Amsterdam Amsterdam- Netherlands [email protected] Ms. Deak Noemi Babes-Bolyai University Cluj-Napoca- Romania [email protected] Ms. Denes E. Eleonora Babes-Bolyai University Cluj-Napoca- Romania [email protected]

Dr. Ehlers W. Andreas University of Amsterdam Amsterdam- Netherlands [email protected] Dr. Eren Tarik Yildiz Technical University Istanbul- Turkey [email protected] Mr. Esfandiarfard Keyhan Uppsala University Uppsala- Sweden [email protected] Prof. Espinosa Arturo University of Murcia Murcia- Spain [email protected] Ms. Feng Man TU Dresden Dresden- Germany [email protected] Mr. Flip Holtrop University of Amsterdam Amsterdam- Netherlands [email protected] Mr. Frost Daniel Sebastian Freie Universität Berlin Berlin- Germany [email protected] Mr. Gese Alexander University of Bonn Bonn- Germany [email protected] Dr. Gaina Luiza-Ioana Babes-Bolyai University Cluj-Napoca- Romania [email protected]


March 20-22

Dr. Gál Emese Babes-Bolyai University Cluj-Napoca- Romania [email protected] Mr. Giese Steven Freie Universität Berlin Berlin-Germany [email protected] Mr. Grell Toni Universitat Leipzig Leipzig- Germany [email protected] Prof. Gudat Dietrich University of Stuttgart Stuttgart-Germany [email protected] Prof. Güzel Bilgehan Çukurova University Adana-Sericam- Turkey [email protected] Ms. Habraken Evi University of Amsterdam Amsterdam- Netherlands [email protected] Ms. Hanf Schirin University of Cambridge Cambridge- UK [email protected] Mr. Harting David TU Dresden Dresden- Germany [email protected] Mr. Hegen Oliver University of Regensburg Regensburg- Germany [email protected]

Dr. Heift Dominikus Durham University Durham- UK [email protected] Ms. Herbay Réka Budapest University of Technology and Economics Budapest- Hungary [email protected] Hereytani Eylül Büşra Çukurova University Adana-Sericam- Turkey [email protected] Prof. Hey-Hawkins Evamarie Universitat Leipzig Leipzig- Germany [email protected] Prof. Hissler Muriel Université Rennes Rennes- France [email protected] Mr. Hoidn Christian University of Regensburg Regensburg-Germany [email protected] Ms. How Rebecca University of St Andrews St Andrews- UK [email protected] Mr. Hoy Reinhard University Leipzig Leipzig- Germany [email protected] Mr. Junker Philip University of Bonn Bonn- Germany [email protected]


March 20-22

Prof. Dr. Kafarski Paweł Wroclaw University of Technology Wroclaw-Poland [email protected] Mr. Kanat Muhammed Yildiz Technical University Istanbul-Turkey [email protected] Prof. Kardas Gulfeza Cukurova University Adana-Sericam- Turkey [email protected] Mr. Kelemen Zsolt Budapest University of Technology and Economics Budapest-Hungary [email protected] Mr. Keweloh Lukas Westfaliche Wilhelms-University Munster Munster-Germany [email protected] Dr. Kilian Petr University of St Andrews St Andres- UK [email protected] Ms. Kirdar Özge Çukurova Unıversıty Adana-Sericam- Turkey [email protected] Mr. Koner Abhishek University of Bonn Bonn-Germany [email protected] Mr. Konrath Robert University of St Andrews St Andrews- UK [email protected]

Mr. Körber Wieland University Leipzig Leipzig- Germany [email protected] Ms. Krachko Tetiana Vrije University of Amsterdam Amsterdam-Netherlands [email protected] Mr. Kunzmann Robert Universität Bonn Bonn- Gemany [email protected] Mr. Lange Merten Westfaliche Wilhelms-University Munster Munster-Germany [email protected] Ms. Leitl Julia University of Regensburg Regensburg- Germany [email protected] Mr. Mai Juri Uppsala University Uppsala-Sweden [email protected] Mr. Maier Thomas University of Regensburg Regensburg- Germany [email protected] Mr. Meissel Hubert Bristol University Bristol- UK [email protected] Ms. Miles-Hobbs Alexandra University of Bristol Bristol-UK [email protected]


March 20-22

Ms. Mistry Krishna Bristol University Bristol- UK [email protected] Ms. Mocanu Olivia Unniv. Rennes 1, Rennes- France [email protected] Ms. Molnár Éva Andreea Babes-Bolyai University Cluj-Napoca- Romania [email protected] Mr. Morales Salazar Daniel Uppsala University Uppsala- Sweden [email protected] Prof. Dr. Müller Christian Freie Universitat Berlin Berlin-Germany [email protected] Ms. Mustieles Marin Irene LCM, Ecole Polytechnique Paris- France [email protected] Assoc. Prof. Nemes Gabriela Babes-Bolyai University Cluj-Napoca- Romania [email protected] Prof. Dr. Nyulaszi László Budapest University of Technology and Economics Budapest-Hungary [email protected] Prof. Orthaber Andreas Uppsala University Uppsala-Sweden [email protected]

Mr. Papke Martin Freie Universität Berlin Berlin- Germany [email protected] Prof. Dr. Peruzzini Maurizio ICCOM-CNR Sesto Fiorentino (Florence) – Italy [email protected] Prof. Dr. Pietschnig Rudolf University of Kassel Kassel-Germany [email protected] Mr. Pleschka Damian Westfaliche Wilhelms-University Munster Munster-Germany [email protected] Mr. Popp John Leipzig University Leipzig- Germany [email protected] Dr. Porumb Dan Babes-Bolyai University Cluj-Napoca- Romania [email protected] Prof. Dr. Pringle G. Paul University of Bristol Bristol-UK [email protected] Mr. Rekhroukh Feriel University of Amsterdam Amsterdam- Netherlands [email protected] Mr. Rigo Massimo Freie Universität Berlin Berlin- Germany [email protected] Mr. Roedl Christian University of Regensburg Regensburg- Germany [email protected]


March 20-22

Dr. Romero Nieto Carlos Institute of Organic Chemistry University of Heidelberg Heidelberg- Germany [email protected] Mr. Sava Alexandru Babes-Bolyai University Cluj-Napoca- Romania [email protected] Mr. Schmer Alexander University of Bonn Bonn- Germany [email protected] Mr. Schoemaker Robin TU Dresden Dresden-Germany [email protected] Mr. Schrader Erik ETH Zurich Zurich-Switzerland [email protected] Mr. Schulz Stephen TU Dresden Dresden- Germany [email protected] Mr. Seitz Andreas-Erich Universitat Regensburg Regensburg-Germany [email protected] Dr. Serrano Ruiz Manuel ICCOM – CNR Florence- Italy [email protected] Mr. Shameem Muhammad Anwar University of Uppsala Uppsala- Sweden [email protected]

Mr. Shuyu Liang ETH Zürich Zurich- Switzerland [email protected] Dr. Slootweg Chris Vrije University of Amsterdam Amsterdam-Netherlands [email protected] Prof. Silaghi-Dumitrescu Luminita Babes-Bolyai University Cluj-Napoca- Romania [email protected] Prof. Stankevic Marek Marie Curie-Sklodowska University Lublin- Poland [email protected] Prof. Dr. Streubel Rainer University of Bonn Bonn-Germany [email protected] Mr. Suhrbier Tim University of Rostock Rostock- Germany [email protected] Dr. Septelean Raluca Babes-Bolyai University Cluj-Napoca- Romania [email protected] Mr. Suteu Razvan Babes-Bolyai University Cluj-Napoca- Romania [email protected] Mr. Tajti Ádám Budapest University of Technology and Economics Budapest-Hungary [email protected]


March 20-22

Ms. Talma Michal Wroclaw University of Science and Technology Wroclaw- Poland [email protected] Mr. Tezcan Fatih Cukurova University Adana-Sericam- Turkey [email protected] Dr. Upmann Daniel TU Braunschweig Braunschweig- Germany [email protected] Dr. Vilotijevic Ivan Friedrich Schiller University Jena Jena- Germany [email protected] Ms. Wanat Weronika University of Technology Wroclaw Wroclaw- Poland [email protected] Mr. Watt Fabian Allan TU Dresden Dresden-Germany [email protected] Prof. Dr. Weigand J. Jan TU Dresden Dresden-Germany [email protected] Mr. Weller Stefan University of Stuttgart Stuttgart- Germany [email protected] Ms. Włodarczyk Katarzyna Marie Curie-Skłodowska University Lublin- Poland [email protected]

Ms. Wojtowicz Natalia Wroclaw University of Science and Technology Wroclaw- Poland [email protected] Prof. Wolf Robert University of Regensburg Regensburg- Germany [email protected] Mr. Wonneberger Peter Universität Leipzig Leipzig- Germany [email protected] Mr. Wossidlo Friedrich Freie Universität Berlin Berlin- Germany [email protected] Mr. Woźnicki Paweł UMCS Lublin Lublin- Poland [email protected] Mr. Yerlikaya Gurbet Cukurova University Adana-Sericam- Turkey [email protected] Prof. Yildiz Emel Cukurova University Adana-Sericam- Turkey [email protected]


2 0 1 7 March 20-22


List of Presenting Authors (O: oral communication, P: poster, PL: plenary lecture)

Last Name First Name Contribution

Acar Ilay Ceren P1

Aysen Demir P44

Bagi Péter P61

Begum Imtiaz P8

Beil Andreas O27

Blum Markus P35

Bockfeld Dirk O3

Boom Devin P22

Botez Laurian O19

Buta Lavinia P49

Buzsáki Dániel O26

Caffyn Andrew P59

Caminade Anne-Marie P2

Chadwick Ailis P29

D´Imperio Nicolas P12

Darendeli Burcu P37

Deak Noemi P28

Denes E. Eleonora P47

Esfandiarfard Keyhan O14

Espinosa Arturo P4

Feng Man P53

Flip Holtrop P54

Frost Daniel Sebastian P45

Gese Alexander P50

Giese Steven O25

Grell Toni P52

Chunxiang Guo P40

Habraken Evi P21

Hanf Schirin O17


2 0 1 7 March 20-22


Harting David P39

Hegen Oliver P19

Herbay Reka P55

Hereytani Eylül Büşra P38

Hissler Muriel PL2

Hoidn Christian P25

How Rebecca P15

Hoy Reinhard P34

Junker Philip P9

Kanat Muhammed O28

Kardas Gulfeza P5

Kelemen Zsolt O8

Keweloh Lukas P8

Kirdar Özge P56

Koner Abhishek O5

Konrath Robert O9

Körber Wieland P42

Krachko Tetiana P23

Kunzmann Robert P17

Lange Merten O7

Leitl Julia P24

Mai Juri P14

Maier Thomas P31

Meissel Hubert O16

Miles-Hobbs Alexandra P30

Mistry Krishna O20

Mocanu Olivia O4

Molnar Eva Andreea P11

Morales Salazar Daniel O1

Mustieles Marin Irene O23

Orthaber Andreas P3

Papke Martin P20


2 0 1 7 March 20-22


Peruzzini Maurizio PL1

Pleschka Damian P6

Popp John O6

Pringle G. Paul PL3

Rekhroukh Feriel P41

Rigo Massimo P18

Roedl Christian O13

Romero Nieto Carlos P60

Sava Alexandru P57

Schmer Alexander P10

Schoemaker Robin P43

Schrader Erik P46

Schulz Stephen O24

Seitz Andreas-Erich O22

Shameem Muhammad Anwar P13

Shuyu Liang P26

Suhrbier Tim O2

Suteu Razvan P48

Tajti Ádám O12

Talma Michal O15

Tezcan Fatih P33

Upmann Daniel P58

Wanat Weronika O18

Watt Fabian Allan P27

Weller Stefan O10

Włodarczyk Katarzyna O21

Wojtowicz Natalia O11

Wonneberger Peter P36

Wossidlo Friedrich P16

Woźnicki Paweł P32

Yerlikaya Gurbet P51

Yildiz Emel P62


2 0 1 7 March 20-22


Location of EWPC14/2017


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2 0 1 7 March 20-22


NOTES


2 0 1 7 March 20-22


book of abstracts - babeș-bolyai universityhetorgmet/ewpc14/assets/docs/abstractewpc.pdf · paul g...

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