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“Andalusia meets Europe II”

ALMERÍA, SPAIN - December 18-21, 2005 http://www.ual.es/GruposInv/FQM-317/meeting/meeting.htm

CIESOL Centro de Estudios Solares

Centro Tecnológico

Andaluz de la Piedra

2nd Workshop of the COST D29/0009/03 Working Group Green Chemistry through Aqueous Organometallic Catalysis

AQUACHEM Midterm Review Meeting and Workshop Transition Metal Chemistry and Catalysis in Aqueous Media

Project RTN n° MRTN-CT-2003-503864

“GREEN CHEMISTRY: A SOLUTION FOR

THE WORLD”

“ANDALUSIA MEETS EUROPE II”

ALMERIA, SPAIN - DECEMBER 18-21, 2005

Location

Dto. Química Física, Bioquímica y Química Inorgánica. Facultad de Ciencias Experimentales, University of Almeria, Spain

La Cañada de San Urbano, s/n 04120 - Almería, Spain

http://www.ual.es/GruposInv/FQM-317/meeting/meeting.htm

Meeting Organization thanks PAI (Junta de Andalucía, FQM-317), MCYT (Spain) for the project PPQ2003-01339, the MCRTN program AQUACHEM (MRTN-CT-2003-503864) and the COST Actions D17 and D29.

Dedicatory:

Víctor Riera (University of Oviedo) Jose Antonio Abad (University of Murcia)

PUBLICATION: Universidad de Almería

ISBN:84-96270-59-9

Legal deposit: AL-4-2006

Local Organizers Dr. Prof. Antonio Manuel Romerosa Nievas (Chairman of the Meeting) Área de Química Inorgánica, Universidad de Almería Phone: +34 950 015305, Fax: +34 950 015008, e-mail: [email protected] Dr. Prof. Agustí Lledós (Co-Chairman of the Meeting) Departament de Química Universitat Autònoma de Barcelona, 08193 Bellaterra(Barcelona) Phone: +34 935811716; Fax: +34 935812920, e-mail: [email protected] External Organizers Prof. Ferenc Joó Coordinator of COST D29/0009/03 WG Institute of Physical Chemistry, University of Debrecen, Hungary Phone: +36 52 512900; Fax: +36 52 512915; e-mail: [email protected] Dr. Maurizio Peruzzini Coordinator of AQUACHEM RTN Networks Research Training Network ICCOM CNR, Florence, Italy Phone: +39 055 5225289; fax: +39 055 5225203; e-mail: [email protected] Congress Secretariat Dr. Sonia Mañas Carpio Área de Química Inorgánica, Universidad de Almería Phone: +34 950 015305, Fax: +34 950 015008, e-mail: [email protected] Dr. Cristobal Saraiba Bello Área de Química Inorgánica, Universidad de Almería Phone: +34 950 015305, Fax: +34 950 015008, e-mail: [email protected]

Local Organizing Commitee Prof. Dr. Vicente Jara Pérez

Prof. Dr. Pedro Gili Trujillo

Prof. Dr. Pablo Antonio Lorenzo Luis

Dr. Christoph Richter

Dr. María de los Angeles Calderon Rodriguez

Mss. Tatiana Campos Malpartida

Mss. Chiara Chiardi

Mr. Chaker Lidrissi

Mrs. Inocenta Mery Mallquil Ayala

Dr. Sonia Mañas Carpio

Mss. Laura Martos Artero

Mrst. Emma Petersen

Mr. Mustapha Saoud

Dr. Cristóbal Saraiba Bello

Mr. Gaspar Francisco Segovia Torrente

Mr. Manuel Serrano Ruiz

The second formal meeting of the COST WG-D29-009/03 will be held in Almería, Spain

from 18th to 21st December of 2005 together with the second annual meeting of the AQUACHEM

RTN project (Transition Metal Chemistry and Catalysis in Aqueous Media, Project RTN n°

MRTN-CT-2003-503864) which will coincide with the Midterm Review meeting of the RTN

project. Professors Antonio Romerosa (Almeria Spain) and Agusti Lledós (Barcelona, Spain) and

their teams are in charge for the organization of both the events which will be held at the

Department of Chemistry of the University of Almeria.

The meeting has been named “Andalusia meets Europe II” and should, in the idea of the

organizers, represent a further important opportunity for scientists coming from the Southernmost

region of Spain to meet and discuss of chemistry and catalysis in water and other ecobenign systems

with some of the leading European experts. This event follows the highly successful meeting

“Andalusia meets Europe I” held in Almeria from September 26th to September 27th, 2003 and

focussed on C-C formation mediated by transition metal complexes. Fostering further

collaborations and strengthening those already existing, is the final target of this meeting and it is

our personal commitment as well.

During the meeting senior scientists of each team funded by both COST and RTN projects

will give a presentation of the research activity carried out by his/her team. These conferences will

be preceded by a few plenary lectures which will be given by invited specialists on green chemistry,

and will be alternated by lectures delivered by outstanding Spanish chemists and young researchers

participating in the twinned projects.

The meeting will represent an occasion to bring together junior and senior researchers from

the groups participating in the activities of the two associated projects with outstanding scientists

and junior researchers from both Spanish and European Universities, particularly, from Andalusia.

For this reason the whole body of these conferences will constitute a unique scientific workshop

named “GREEN CHEMISTRY: A SOLUTION FOR THE WORLD”. This will constitute the

first of a series of events aimed at making the point on hot topics with high impact in the area of

“green chemistry”, particularly, experimental and theoretical methods for chemistry and catalysis in

water and other ecobenign systems.

Antonio Romerosa and Agustí Lledós

Chairmen of the meeting

Structuring the European Research Area

Human Resources and Mobility

Marie Curie Actions

General objectives

The overall strategic objective of the Human Resources and Mobility activity is to provide

broad support for the development of abundant and dynamic world-class human resources in the

European research system, taking into account the inherent international dimension of research.

With a view to the successful creation of the European Research Area, the Human

Resources and Mobility activity involves a coherent set of actions, largely based on the financing of

structured mobility schemes for researchers. These are essentially geared to the development and

transfer of research competencies, the consolidation and widening of researchers' career prospects,

and the promotion of excellence in European research. All actions under this activity are named

“Marie Curie” actions. Among these one can find the Host-driven actions, the Individual-driven

actions, the Excellence Promotion and Recognition, the Return and Reintegration Mechanisms and

the Cooperation with Member States and Associated Countries.

Marie Curie Host-driven actions

These actions are aimed at supporting research networks, research organisations and

enterprises (including in particular SMEs), in the provision of structured global schemes for the

transnational training and mobility of researchers, and the development and transfer of

competencies in research including complementary skills (research programme management, ethics,

communication, career development, etc). The actions concerned are intended to have a strong

structuring effect on the European research system, in particular by encouraging junior researchers

to pursue a research career.

The line of action “Host-driven actions” is implemented by the MC Research Training

Networks, the MC Host Fellowship for early Stage Research Training, the MC Host Fellowship for

transfer of Knowledge and the MC Conferences and training Courses.

The Research Training Networks provide the means for research teams of recognised international

stature to link up, in the context of a well-defined collaborative research project, in order to

formulate and implement a structured training programme for researchers in a particular field of

research. Networks will provide a cohesive, but flexible framework for the training and professional

development of researchers, especially in the early stages of their research career. Networks also

aim to achieve a critical mass of qualified researchers, especially in areas that are highly-

specialised and/or fragmented; and to contribute to overcoming institutional and disciplinary

boundaries, notably through the promotion of multidisciplinary research. They will also provide a

straightforward and effective means to involve the less-favoured regions of the EU and Associated

Candidate Countries in internationally recognised European research co-operation.

Projects supported in this action will have to exploit the network structure to the best extent

possible, typically combining local specialist training with network-wide,

interdisciplinary/intersectorial training and research activities. The joint collaborative research

training projects will aim at increasing the number of researchers in areas where there is an

identified training need, addressing one or more of the following:

• Integrating different disciplines - bringing together and integrating different disciplines,

especially towards the derivation of novel concepts, approaches and frameworks;

• Industry-academia cooperation - establishing or furthering co-operation in research and research

training between academia and industry and/or other relevant economic actors;

• Overcoming fragmentation - overcoming fragmentation in areas where there is a lack of pan-

European collaboration and integration or where the scientific community is too small and or

dispersed to achieve a critical mass in research and research training, potentially hindering a

significant advancement in knowledge.

Particular attention will be paid to the genuine integration in the networks of teams from the

new Member States, Candidate and other Associated Countries, and other Less Favoured Regions

of the EU.

Implementation

Participants

A participant in this action is an organisation that is a member of a network selected by the

Commission and that recruits eligible researchers or directly contributes to the research and training

project of the network.

A network in this action shall be composed of at least three participants (e.g. universities,

research centres, companies, SMEs) established in at least three Member or Associated States from

which two must be Member or Associated Candidate Countries. However, it is anticipated that a

network will normally consist of a larger number of participants.

Projects

The joint collaborative research project undertaken by the network is to provide a platform

for training, for the transfer of knowledge and for career development of the researchers recruited in

the frame of the network. The researchers are therefore to be fully integrated into the research by

involving them, for example, in exchanges between teams, network meetings, collaborative

research or the dissemination of results. In this context, participants will also need to develop a

structured programme for training (e.g. courses, seminars, intersectorial training periods, training in

research management and exploitation of research results) and mentoring (e.g. supervision, career

guidance) to the benefit of all researchers recruited by the network.

Participants will be given significant autonomy and flexibility in the detailed operation of

the network.

The size of the project and of the network will depend on the nature and scope of the

research and training activities to be undertaken by the network, as well on considerations regarding

management and effective interaction among the participants. Based on the experiences of the first

call for Research Training Networks in the Sixth Framework Programme, most networks have a

project duration of 4 years, a number of participants ranging from 6 to 14, and an overall

approximate budget ranging from € 1 500 000 to € 3 000 000.

Eligible Researchers1

This action will be directed at early stage researchers, for the purpose of initial training

(including within the frame of doctoral studies) while experienced researchers will be eligible

with respect to the needs of transfer of knowledge in the project. Researchers with more than 10

years of research experience (full-time equivalent), counting from the time the degree/diploma was

obtained giving access to embark on a doctorate2 in the country where it has been awarded, will

not be eligible for selection.

Projects that are clearly multi-/interdisciplinary, intersectoral and/or genuinely leading-edge

might require a larger proportion of experienced researchers; otherwise networks are to concentrate

on early stage researchers.

Each researcher will establish, together with his/her personal supervisor, a Personal Career

Development Plan comprising his/her training needs and scientific objectives and later on report

upon the success with which these objectives were met. In this way the researchers will be

encouraged to play an active role in shaping their own training programme and professional

development.

The training opportunities for researchers within the coherent training and mobility scheme

provided by the project may range from 3 months to 3 years.

In the case of a researcher being seconded to another participant for a period of more than 30

% of the total period of recruitment, he/she will have to be recruited by this other participant.

Purpose of the Mid-Term Review:

The Mid-Term Review meeting is an opportunity for the network to take stock of progress

to date, to explore flexibility in the contract and to clarify many issues (financial, administrative,

best working practice, progress with engagement of early-stage and experienced researchers) with

the Commission and to subsequently change course if necessary. It is principally an opportunity for

the partners, the recruited ESR and ER and the representative(s) of the Commission to discuss

questions or issues which may not be clear from the official documentation or the contract. As such,

1 The definitions applicable to eligible researchers are given in point 2.5.3.

2 The degree must entitle the holder to embark on doctoral studies, without having to acquire any further qualifications.

it is not just a scientific evaluation of the Network nor should it be the first point in the course of the

contract at which problems are brought to the attention of the Commission. Particular attention is

paid to the training and networking aspects. The structure of the network and the contract’s work

programme will also be reviewed and, if necessary, contract modifications defined. The Mid-Term

Review is a valuable source of feedback to the RTN management.

Program of the meeting

COST D29

SUNDAY DECEMBER 18th, Vincci Mediterraneo Hotel, Almería, Spain

Arrival at Almería.

h 15:30 Registration. Vincci Mediterraneo Hotel

h 16:30 Meeting of the participants and informal discussion

h 16:45 Welcome speech from the Chairman ANTONIO ROMEROSA

h 16:55 Welcome speech by:

Rector (Universidad de Almería).

Jaume Casabó (Presidente del Grupo Especializado de Química

Inorgánica. Real Sociedad Española de Química).

h 17:20 Opening remarks by the COST D29 WG009/003 coordinator

FERENC JOO

First scientific session

h 17:50 – 19:00 General discussion of the activity of the Working Group and

information concerning the situation of COST Action D29

F. Joó (University of Debrecen, Hungary)

h 20:00 Reception. Vincci Mediterraneo Hotel.

MONDAY DECEMBER 19th, University of Almería, Spain

COST D29 MEETING & AQUACHEM 2nd YEAR MEETING

Second scientific session

h 9:00 – 9:50 José Gimeno. (University of Oviedo, Spain)

“New ruthenium catalysts in aqueous media: competitive applications

in organic synthesis”

h 9:50 – 10:15 Antonio Romerosa. (Team UAL, (AQUACHEM + COST) Almería,

Spain)

“New non classical water soluble vinylidene ruthenium complexe:

reactivity and catalytic properties”

h 10:15 – 10:40 Rinaldo Poli. (Team LCC CNRSb, (AQUACHEM + COST)

Toulouse, France)

“Aqueous reduction chemistry of compound Cp*2Mo2O5: generation

and characterization of a mixed oxo-hydroxo triangular cluster with an

unusual electronic structure”

h 10:40 – 11:05 Alexander M. Kirillov. (Team IST; AQUACHEM, Lisbona,

Portugal)

“New water-soluble multinuclear copper triethanolamine complexes

as efficient catalysts for mild peroxidative oxidation of alkanes in

aqueous biphasic liquid medium”

h 11:05 – 11:30 Coffee break

Third scientific session

h 11:30 – 11:55 Antonio Fernández Barbero. (Univesidad de Almería, Spain).

“Discontinuous phase transition of thermosensitive microgel particles”

h 11:55 – 12:20 Ovadia Lev. (Team HUJI; AQUACHEM, Jerusalem, Israel).

“Distribution of Polysulfides in aqueous solutions”

h 12:20 – 12:45 Ferenc Joó. (Team UD; (AQUACHEM + COST) Debrecen,

Hungary).

“Recent results of the UD team in aqueous organometallic catalysis”

h 13:00 – 15:00 Lunch

Fourth scientific session

h 15:00 – 15:25 Chiara Ciardi (Team UAL, (AQUACHEM + COST) Almería, Spain)

“Synthesis of New Chiral Water soluble Phosphines from Naturally

Occurring Amino Acids”

h 15:25– 15:50 Abel Moreno. (Instituto de Químicas, UNAM; México)

"The effects of electric and magnetic fields on the 3D structure of

biological systems in aqueous/gel solutions"

h 15:50 – 16:15 Luca Gonsalvi. (Team CNR; (AQUACHEM + COST) Florence,

Italy).

“Water soluble Ru and Rh complexes for selective oxidations and

hydrogenations”


Fifth scientific session

h 16:45 – 17:10 (a) Luisa Martins. (Team IST; AQUACHEM, Lisbona, Portugal).

"Synthesis of new tris(pyrazolyl)methanesulfonate complexes in

aqueous medium"

Elisabete C.B.A. Alegria, Luísa M.D.R.S. Martins, Telma F.S. Silva

and Armando J.L. Pombeiro.

(b) Elisabete Alegria. (Team IST; AQUACHEM, Lisbona, Portugal).

"Peroxidative oxidation of cyclohexane in aqueous medium by

rhenium and iron complexes ".

Elisabete C.B.A. Alegria, Luísa M.D.R.S. Martins and Armando J.L.

Pombeiro.

h 17:10 – 18:00 POSTERS SESSION.

h 18:00 – 19:00 Round table with flash presentations of the young participants (10

min each) from the different groups and discussion of the scientific

results. Chairman M. Peruzzini

h 20:00 Reception by City Hall at “Baños Árabes” (IX century monument)

TUESDAY DECEMBER 20th, University of Almería, Spain

COST D29 MEETING & AQUACHEM 2nd YEAR MEETING

Sixth scientific session

h 9:00 – 9:50 Christian Bruneau. (University of Rennes. Rennes, France)

“Rhodium and ruthenium precursors For selective catalytic transformations”

h 9:50 – 10:15 Maurizio Peruzzini. (ICCOM CNR, Florence, Italy)

Introductory remarks concerning the AQUACHEM consortium

h 10:15 – 10:40 Anne Marie Caminade. (Team LCC CNRSa ; AQUACHEM,

Toulouse, France)

"Organometallic derivatives of phosphorus dendrimers"

A.M. Caminade, R. Laurent, P. Servin, J.P. Majoral

h 10:40 – 11:05 Jenny Gun. (Team HUJI; AQUACHEM, Jerusalem, Israel)

"Analytical and electroanalytical applications of siderophores"


Seventh scientific session

h 11:30 – 11:55 Agustí Lledós. (Team UAB. AQUACHEM, Barcelona, Spain)

"Computational modelling of reaction mechanisms in aqueous media"

h 11:55 – 12:20 Zeric Snezana. (University of Belgrade, Servia)

“Study of CH/π interactions in acetylacetonato complexes”

h 12:20 – 12:45 Joo Eu Jeen. (Team UEN, AQUACHEM, Erlangen, Germany)

“Activation of peroxides by heme and non-heme Fe(III) complexes”

h 13:00 – 15:00 Lunch

Eighth scientific session

h 15:00 – 15:25 a) Mathew Herbert. (University of Sevilla, Spain)

"Poly(dimethylsiloxane) chains as solubilisiers of Cu Complexes in

supercritical carbon dioxide"

b) Gabor Papp (Team UD; (AQUACHEM + COST) Debrencen,

Hungary)

“New Classical and Non-Classical Hydrides of Ru(II) in Aqueous

Solutions”

h 15:25– 15:50 Armando J. L. Pombeiro. (Team IST; AQUACHEM, Lisbon,

Portugal).

"Chemistry in Aqueous medium at the IST Group: Overall View"

h 15:50 – 16:15 Natalia Belkova. (Team INEOS; AQUACHEM, Moscow, Russian).

“Spectroscopic and theoretical studies of the solvent influence on the

proton transfer to transition metal hydrides"

E. Shubina, N. Belkova.


Ninth scientific session

h 16:45 – 17:20 Dr. Eric Manoury and Dr. Agnes Labande. (Team LCC CNRSb,

Toulouse, France).

"New ferrocenyl ligands for (asymmetric) catalysis: candidates for

catalysis in aqueous media?"

h 17:20 – 17:40 Amadeo Rodríguez. (Universidad de Almería, Almería, Spain).

Responsable of CIESOL (Solar Institute).

“The CIESOL a research centre to find new applications for the sun”

h 17:40 – 19:00 Visit to CIESOL institute.

h 21:30 Social Dinner in a typical Andalusia Restaurant

WEDNESDAY DECEMBER 21st, University of Almería, Spain

AQUACHEM MIDTERM REVIEW MEEETING

Program defined in collaboration with

the EC Scientific Officer in charge of the RTN Network

h 9:00 – 9:15 Dr. Sergio di Virgilio (Scientific Officer, European Commission,

Brussels, Belgium)

General introduction

h 9:15 – 9:45 Dr. Maurizio Peruzzini (ICCOM CNR, Florence, Italy)

Activity and perspectives of the AQUACHEM network

h 9:45 – 10:00 Team ICCOM CNR (Florence, Italy). Dr Maurizio Peruzzini

“An overview of the work done in Florence within the AQUACHEM

project. Chemistry and catalysis in water”

V. Landaeta, L. Gonsalvi, M. Peruzzini

Presentation of ICCOM CNR team (expertise and activity)

h. 10:00 – 10:25 Team LCC CNRS (Toulouse, France) Mr Paul Servin,

“Organometallic catalysts in aqueous media. The use of dendritic PTA

ligands”

P. Servin, R. Laurent, A.M. Caminade, J.P. Majoral

h. 10:25 – 10:30 Team LCC CNRS (Toulouse, France) Dr Anne Marie Caminade,

Presentation of LCC/a team (expertise and activity)


h. 11:00 – 11:25 Team LCC CNRS (Toulouse, France) Ms Chiara Dinoi,

“Reactions of hemimetallocenic molybdenum (VI) complexes with

Sulfur Compounds”

C. Dinoi, R. Poli, J.-C. Daran, M. Baya, F. Demirhan, G. Taban

h. 11:25 – 11:30 Team LCC CNRS (Toulouse, France) Prof Rinaldo Poli,

Presentation of LCC/b team (expertise and activity)

h 11:30 – 11:55 Team UD (Debrecen, Hungary) Dr W. Wojtków

“Reactions of alkynes in formic acid”

F. Joó, W. Wojtkov

h. 11:55 – 12:00 Team UD (Debrecen, Hungary) Prof Ferenc Joó,

Presentation of UD team (expertise and activity)

h 12:00 – 12:25 Team HUJI (Jerusalem, Israel). Dr Petr Prikhodchenko,

“EC/ESI-MS studies of transition metal complexes”

P. Prikhodchenko, J. Gun, V. Gutkin

h. 12:25 – 12:30 Team HUJI (Jerusalem, Israel) Prof Ovadia Lev,

Presentation of HUJI team (expertise and activity)

h 12:30 – 12:55 Team UAB (Barcelona, Spain). Dr Andrea Rossin

“Selectivity of C=O hydrogenation in alpha,beta-unsaturated

aldehydes with Ru(I) water-soluble complexes: A computational

analysis"

A. Rossin, G. Kovács, G. Ujaque, A. Lledós, F. Joó

h. 12:55 – 13:00 Team UAB (Barcelona, Spain) Prof Agusti Lledos,

Presentation of UAB team (expertise and activity)

h 13:00 – 13:25 Team YoK (York, UK) Dr Nicole Reddig

“The excited dynamics of molybdate sensors and the structure of the

molybdate-rhenium sensor complex”

h. 13:25 – 13:30 Team YoK (York, UK) Prof Robin Perutz,

Presentation of YORK team (expertise and activity)

h 13:30 – 13:55 Team UEN (Erlangen, Germany) Ms. Joo-Eun Jee.

Comparative Study of the Interaction of NO with Water Soluble

Cationic- and Anionic FeIII Porphyrins

Joo-Eun Jee, Maria Wolak, Achim Zahl and Rudi van Eldik

h. 13:55 – 14:00 Team UEN (Erlangen, Germany) Ms. Ariane Brausam,

Presentation of UEN team (expertise and activity)

h 14:00 – 15:30 Lunch

h 15:30 – 15:55 Team IST (Lisbon, Portugal) Mr Yahuen Karabach

"New 1D and 2D water-soluble Cu(II) polymers derived from

pyromellitic acid"

E.Yu. Karabach, M.F.C. Guedes da Silva, M. Haukka, A.M. Kirillov,

M.N. Kopylovich and A.J.L. Pombeiro

h. 15:55 – 16:00 Team IST (Lisbon, Portugal) Prof. Armando Pombeiro,

Presentation of IST team (expertise and activity)

h 16:00 – 16:25 Team UAL (Almeria, Spain). Ms Inocenta Mery Mallqui Ayala

“New water soluble allenylidene ruthenium complexes including the

Cp(CONC(CH3)3)2 ligand”

A. Romerosa, I. M. Mallqui Ayala, M. Serrano-Ruiz

h. 16:25 – 16:30 Team UAL (Almeria, Spain) Prof. Antonio Romerosa,

Presentation of UAL team (expertise and activity)

h 16:30 – 16:55 Team INEOS (Moscow, Russia). Dr Natalia Belkova.

"Intermolecular Hydrogen Bonding Between Neutral Transition Metal

Hydrides (CpM(CO)3H, M = Mo, W) and Bases"

N. Belkova, O. Filippov, V. Levina, E. Gutsul, L. Epstein, E. Shubina

h. 16:55 – 17:00 Team INEOS (Moscow, Russia) Prof. Elena Shubina,

Presentation of INEOS team (expertise and activity)


h 17:30 – 18:00 Meeting of the EC Officer with Young Scientists of the AQUACHEM

network (Restricted participation)

h 18:00 - … Conclusions from the EC Officer and the AQUACHEM Coordinator

Round table about the perspectives and ideas for future collaborations

and future meetings. Closing notes.

TABLE OF CONTENTS

PLENARY LECTURES …………………………………… 1

ORAL COMMUNICATIONS …………………………….. 4

POSTERS ……………………………………………………39

LIST OF PARTICIPANTS …………………………………60

AUTHOR’S INDEX …………………………………………65

PLENARY LECTURES

AQUACHEM & COST D-29

2

PL-1- NEW RUTHENIUM CATALYSTS IN AQUEOUS MEDIA: COMPETITIVE APPLICATIONS IN ORGANIC SYNTHESIS

José Gimeno Departamento de Química Orgánica e Inorgánica. Instituto de Química Organometálica

“Enrique Moles”. Facultad de Química. Universidad de Oviedo. 33006 Oviedo. E-mail: [email protected]

Water is no longer considered a contaminant in modern Organic Chemistry. New

approaches carried out in aqueous media have disclosed synthetic routes providing very competitive alternatives to the traditional methodologies using organic solvents.1 In particular, catalytic transformations in water which proceed with high efficiency and selectivity have become a field of prevalent interest since they combine the economy of the processes with an environmental friendly synthetic methodology. 2

However, despite the large number of catalytic applications of ruthenium complexes in organic synthesis only a few examples of active catalysts in water are known. We have recently started to study the catalytic activity in aqueous media of bis(allyl)ruthenium(IV) and (η 6-arene)ruthenium(II) derivatives (see Figure).This lecture will deal with the applications to the following transformations:

i) Isomerization of allylic alcohols into carbonyl compounds ii) One-pot isomerization of allylamines which lead to primary or secondary

amines via deprotection of the amine by liberating the allyl moiety. iii) Reduction of allyl alcohols into saturated alcohols through a tandem process

involving an isomerization followed by a hydrogen transfer reaction

A wide scope of substrates has been studied. The catalytic transformations not only proceed very efficiently but also in a chemoselective manner showing the excellent catalytic performance of these catalysts. Since some of them can be recycled these complexes are illustrative examples of suitable catalysts in aqueous media of interest to develop “clean” industrial organic processes.

Ru

Cl

Cl

Ru

Cl

Cl

Cl

Ru

Cl

PPhn(OCH2CH2NMe3)3-n

RuClCl

[SbF6]n

n = 0, 1 or 2

______________ References:

1. See for instance: C.J. Li, Chem. Rev., 1993, 93, 2023. C.J. Li, T.H. Chan, Organic Reactions in Aquoeus Media John Wiley &Sons: New York, 1997. U.M. Lindström Chem. Rev. 2002, 102, 2751. C-J. Li, Chem. Rev. 2005, 105, 3095. 2. B. Cornills, W.A. Herrmann Eds. Aqueous-Phase Organometallic Catalysis: Concepts and Applications Wiley-VCH: Wheinheim,2nd. Edition 2004. F.Joó, Aqueous Organometallic Catalysis, Kluver: Dodrecht, 2001. 3. C. Bruneau, P.H. Dixneuf, Eds. Ruthenium Catalysts and Fine Chemistry, Springer: Berlin, 2004. S.-I. Muráhashi, Ed. Ruthenium in Organic Syínthesis Wiley-VCH: Wheinheim, 2004. 4. V.Cadierno, S.E. García-Garrido, J. Gimeno, Chem. Commun. 2004, 232. V.Cadierno, S.E. García-Garrido, J. Gimeno J. Am. Chem. Soc. 2005, in press. V.Cadierno, S.E. García-Garrido, J. Gimeno, N. Nebra Chem. Commun. 2005, 4086. P. Crochet, J. Díez, M. Fernandez, J. Gimeno, Adv. Synth. Catal. 2005, in press.


3

PL-2- RHODIUM AND RUTHENIUM PRECURSORS FOR SELECTIVE CATALYTIC TRANSFORMATIONS

Christian Bruneau

Institut de Chimie, UMR 6509: CNRS-Université de Rennes 1, “Organometallics and catalysis”,

263 avenue du Général Leclerc 35042 Rennes Cedex. E-mail: [email protected]

Metal catalysis makes possible the selective preparation of building blocks of

high potential in synthesis of biologically active compounds and intermediates. Three examples will be discussed : - the enantioselective hydrogenation of β-enamido esters catalyzed by rhodium

complexes containing optically pure bidentate phosphine1 or monodentate phosphite ligands.2

OR

N OH

O

H2

OR

N OH

O

[Rh(cod)(P P*)]BF4

P P* = Duphos, BPEe.e. up to 94%

- the regio- and enantioselective allylic substitution of unsymmetrical substrates in

the presence of [Cp*Ru(L*2)(MeCN)]PF63,4 and in situ generated ruthenium

catalysts.5

Ph X Ph

Nu

X= OCO2Et, Cl

+ NuH

NuH= phenol, amineC-nucleophiles

e.e. up to 85%

[Cp*Ru(MeCN)3]PF6+ chiral bisoxazoline

- the selective hydrogenation/monoreduction of functionalized cyclic imides in water to form lactams by using molecular ruthenium complexes as catalysts precursors.6

NH

O

O

Ru cat.

H2O, H2

NH

O

H

H

______________ References:

1. Jerphagnon, T.; Renaud, J.-L.; Demonchaux, P.; Ferreira, A.; Bruneau, C. Tetrahedron : Asymmetry, 2003, 14, 1973-1977. 2. Jerphagnon, T.; Renaud, J.-L.; Demonchaux, P.; Ferreira, A.; Bruneau, C. Adv. Synth. Catal., 2004,

346, 33-36. 3. Mbaye, M. D.; Demerseman,B.; Renaud, J.-L.; Toupet, L.; C. Bruneau, C. Angew. Chem. Int. Ed. 2003,

42, 5066-5068. 4. Mbaye, M. D.; Demerseman,B.; Renaud, J.-L.; Toupet, L.; C. Bruneau, C. Adv. Synth. Catal., 2004,

346, 835-841. 5. Mbaye, M. D.; Demerseman,B.; Renaud, J.-L.; C. Bruneau, C. Chem. Commun., 2004, 1870-1871. 6. Aoun, R.; Renaud, J.-L.; Dixneuf, P. H.; Bruneau, C. Angew. Chem. Int. Ed., 2005, 44, 2021-2023.

ORAL COMMUNICATIONS


5

C-1- NEW NON CLASSICAL WATER SOLUBLE VINYLIDENE RUTHENIUM COMPLEX: REACTIVITY AND CATALYTIC

PROPERTIES

Antonio Romerosa, Tatiana Campos-Malpartida

Área de Química Inorgánica. Universidad de Almería, 04120, Almería,Spain E-mail. [email protected].

Despite the great interest for water soluble, catalytically efficient, metal complexes, not many examples of such compounds have been so far described. This result is quite surprising in view of the intense research activity centred on hydrosoluble metal complexes and the pressing request for developing more and more environmentally benign technologies in manufacturing of fine chemicals.[1] We have recently started working in this hot area of chemistry and have demonstrated that: (i) ruthenium vinylidenes and allenylidenes stabilised by the water soluble phosphine mTPPMS (mTPPMS = m-sulphonatedtriphenylphosphine) efficiently catalyzes the ROMP of cyclic alkenes [2] and, (ii) the water soluble ruthenium complex [CpRuCl(PTA)2] (PTA = 1,3,5-triaza-7-phosphaadamantane) brings about the selective hydrogenation of benzylidene acetone in water.[3,4] As a further step forward in this area, we report here the synthesis and the characterization of a new water soluble vinylidene of formula [CpRu(=C=CHPh)LL’]n (L= PPh3; L’ = mPTA) (mPTA = methyl-1,3,5-triaza-7-phosphaadamantane), which shows interesting non classical chemistry toward nucleophilic molecules in both water and biphasic aqueous conditions.

______________ References: 1. R. H. Grubbs, in Aqueous Organometallic Chemistry and Catalysis, I. T. Horváth, F. Joó, Eds.; NATO ASI Ser. 3 5; Kluwer Academic Publishers, Dordrecht, The Netherlands, 1995, p. 15. 2. M: Saoud et al. Organometallics, 2000, 19, 4005-4007. 3. S. Bolaño et al J. Mol Cat. 2004, 224, 61-70. 4. D. Akbayeva et al, Chem. Comm. 2003, 264-265. Acknowledgements:

Thanks are given to PAI (Junta de Andalucía, FQM-317), MCYT (Spain) for the project PPQ2003-01339, the MCRTN program AQUACHEM (MRTN-CT-2003-503864) and the COST Actions D17 and D29.


6

C-2-AQUEOUS REDUCTION CHEMISTRY OF COMPOUND Cp*2Mo2O5: GENERATION AND CHARACTERIZATION OF A MIXED OXO-HYDROXO TRIANGULAR CLUSTER WITH AN

UNUSUAL ELECTRONIC STRUCTURE Funda Demirhan*,a Bahar Çagatay,a Deniz Demir,a Miguel Baya,b Jean-Claude

Daranb and Rinaldo Polib

a Celal Bayar University, Faculty of Sciences & Liberal Arts, Department of Chemistry, 45030, Muradiye-Manisa, Turkey

b Laboratoire de Chimie de Coordination, UPR CNRS 8241, 205 Route de Narbonne, 31077 Toulouse cedex, France. E-mail: [email protected]

The reduction of Cp*2Mo2O5 with Zn in a MeOH-H2O solution that is acidified

with either CF3COOH or CF3SO3H leads to the formation of [Cp*3Mo3(µ-O)2(µ-OH)4]2+ ion as a trifluoroacetate or trifluoromethylsulfonate salt. The structure of the compound is confirmed by X-ray analyses. The anions establish hydrogen-bonding interactions with all four bridging OH groups. DFT calculations afford bonding parameters in close agreement with the observed structure and indicate that the cluster is best described as a valence-delocalized Mo313+ species. The 5 metal electrons are distributed among an a-type (z2) orbital, which insure most of the metal-metal attraction, and two essentially metal-metal nonbonding e-type (xy) orbitals with a slight Mo-(µ-O) π*-type contribution. Because of the C2 symmetry, the latter orbitals are not degenerate. The calculations show that the unpaired electron is located in a MO with equal contribution from two Mo atoms, in agreement with the experimental observation of coupling of the unpaired electron to two Mo atoms in the isotropic EPR spectrum.


7

C-3- NEW WATER-SOLUBLE MULTINUCLEAR COPPER TRIETHANOLAMINE COMPLEXES AS EFFICIENT CATALYSTS

FOR MILD PEROXIDATIVE OXIDATION OF ALKANES IN AQUEOUS BIPHASIC LIQUID MEDIUM

Alexander M. Kirillov,a Maximilian N. Kopylovich,a Marina V. Kirillova,a Yauhen

Yu. Karabach,a Matti Haukka,b M. Fatima C. G. da Silva,a

Armando J. L. Pombeiro a

a Centro de Quimica Estrutural, Complexo I, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001 Lisbon, Portugal; E-mail: [email protected], [email protected]

b University of Joensuu, Department of Chemistry, P.O. 111, FIN-80101, Joensuu, Finland

Copper containing catalysts are of a high potential interest, since Cu is a cheap

and widespread metal in nature, present in the active sites of many enzymes, including the particulate methane monooxygenase (pMMO), found in methanotrophs, with a tri- or a multinuclear Cu cluster that catalyzes oxidation of alkanes and olefins. Although increasing attention has been paid to design Cu complexes as models of proteins, the use of multicopper complexes for such reactions still remains an unexplored field of research. Hence, our main aims are to find a simple synthetic method for multinuclear Cu complexes with N,O-ligands and to search for their catalytic activity in alkane oxidations under mild conditions.

Herein we report the easy self-assembly synthesis at room temperature of Cu(II) triethanolamine complexes of diverse nuclearity. Namely mono-, di-, tri-, tetra- and polynuclear complexes are obtained by reactions in aqueous solution, of a copper salt with triethanolamine and sodium azide, benzoic acid, 4-hydroxybenzoic acid, sodium tetrafluoroborate or terephthalic acid. All the compounds have been isolated as crystalline solids and characterized by IR and FAB+-MS spectroscopies, elemental and X-ray diffraction analyses.1

The obtained Cu complexes act as catalysts or catalyst precursors for the oxidation of liquid (C6H12) and gaseous (CH4, C2H6) alkanes to the corresponding alcohols and ketones, by aqueous H2O2 in MeCN/H2O medium at room temperature, and with some advantages over the current industrial synthetic processes.1,2 For cyclohexane oxidation, the effects of various parameters have been investigated in a systematic way and allowed to achieve, in a single batch, yields of cyclohexanol and cyclohexanone (based on alkane) and TONs of ca. 39% and 380, respectively, with selectivity towards the main products close to 100%, corresponding, to our knowledge, to the most active and selective Cu systems so far reported for that alkane oxidation reaction. The catalysts can be reused upon recycling and, at least the tetranuclear one maintains almost the same level of activity even after five consecutive cycles. Moreover, Cu complexes appear to exhibit an activity that is comparable to, or even higher than that of pMMO, e.g. 17, 34 and 97 nmol of EtOH, MeOH and C6H11OH+C6H10O per min·mg of catalyst, respectively, versus 12−17 nmol of EtOH per min·mg of pMMO for the enzymatic hydroxylation of ethane, a particularly favorable substrate. Other advantages of these catalytic systems include their simple and cheap synthesis and/or the use of easily available and environmentally tolerable starting materials.1,2


8

This work has been partially supported by the Human Resources and Mobility Marie Curie Research Training Network (AQUACHEM project, CMTN-CT-2003-503864) and the Foundation for Science and Technology (FCT), and its POCTI programme (FEDER funded).

______________ References: 1. Kirillov, A. M.; Kopylovich, M. N.; Kirillova, M. V.; Haukka, M.; da Silva, M. F. C. G.; Pombeiro,

A. J. L. Angew. Chem. Int. Ed., 2005, 44, 4345. 2. Pombeiro, A. J. L.; Kirillov, A. M.; Kopylovich, M. N.; Kirillova, M. V.; Haukka, M.; da Silva, M. F.

C. G. Patent pending PT 103225 (2005/01/19).


9

C-4- VOLUME PHASE TRANSITION OF MICROGEL PARTICLES

Antonio Fernández-Barbero

Department of Applied Physics, University of Almería, 04120-Almería, Spain

E-mail: [email protected]

Thermo-sensitive poly(NIPAM) polymer networks forming a gel exhibit reversible discontinuous volume phase transitions at a lower critical solution temperature (LCST) around 32 ºC. Transition results from the competition between repulsive intermolecular forces responsible for the solvency of the polymer, the network elasticity arising mainly from the cross-links between polymer chains and attractive components coming from hydrogen bonds. However, when the gel dimension is reduced to the colloidal length scale, the volume phase transition becomes always continuous, under the same external and environmental conditions. This transition has been extensively studied during the last few years [see for instance 1-3].

In the present work we show that under special circumstances, the volume transition may also be discontinuous for microgels. This result is supported by light scattering and micro-calorimetric measurements. A summary of previous results will be also shown to introduce the audience to the swelling of micro particles. ______________ References: 1. Férnandez-Nieves, A.; Fernández-Barbero, A.; Vincent, B.; De las Nieves, F. J. Macromolecules, 33 (2000) 2114. 2. Kratz, K.; Hellweg, T.; Eimer, W. Polymer 42 (2001) 6631-6639. 3. A. Fernandez-Barbero, A. Fernandez-Nieves, I. Grillo, E. Lopez-Cabarcos, Phys. Rev. E, 66 (2002) 51803. Acknowledgments: Financial support by Spanish Government and European Union under project, MAT2003-03051-C03-01.


10

C-5- IRON SIDEROPHORE RESEARCH IN HUJI

Jenny Gun, Artem Melman, Constant M.G. van den Berg, and Ovadia Lev

Casali Institute of Applied Chemistry, Department of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel. E-mail: [email protected]

Iron is an abundant element, essential for virtually all life forms. Considerable

research activity is stimulated by the biological role of iron ligands, and there is considerable siderophore research aiming at the development of analytical and catalytic applications and bioapplications. Our recent activities in this field centre on two lines of research: the first involves the development of a new potent class of tridentate iron ligands (bis(hydroxyamino)-1,3,5-triazines (BHTs), and the second involves development of iron siderophores for catalytic cathodic stripping analysis of iron in seawater.

A new versatile family of chelating agents based on bis(hydroxyamino)-1,3,5-triazines, BHTs was synthesised and their chelating properties were investigated by electrochemistry, spectroscopy and titrimetry revealing high redox stability, transparency in the visible range, and diprotic acid–like behaviour in the 5 - 9 pH range. The iron(III) and iron(II) - BHT complexes were studied revealing high affinity of BHTs to iron(III). Electrochemical studies show exceptional preference of the BHT ligands to iron(III) over iron(II), this, in addition to their small size and their fast and reversible electrochemistry make them potentially useful electrochemical redox couples for the low end of the aqueous potential window ( < 0.6 V, vs NHE). The synthetic versatility of the new ligands allows easy tuning of the hydrophobicity, redox potential, and to some extent the stability constant of the complexes by alteration of the peripheral groups appended to the BHTs.

A procedure is developed for the determination of trace level iron in natural waters by catalytic cathodic stripping voltammetry using a solid electrode consisting of a gold microwire coated with mercury in the presence of adsorbed or dissolved catechol moieties. The mercury coated micro electrode was reactivated electrochemically by briefly applying a very negative potential (-3 V) for 2s which caused the electrode to be stable for at least a week without having to replate the mercury. The limit of detection for iron (~0.15 nM with a 60 s adsorption time) is sufficient to determine iron in seawater. The siderophore - microwire electrode can be readily fitted in a flow cell and used for flow analysis of iron.


11

C-6- RECENT RESULTS OF THE UD TEAM IN AQUEOUS ORGANOMETALLIC CATALYSIS

Ferenc Joó

Institute of Physical Chemistry, University of Debrecen and Research Group of Homogeneous

Catalysis of the Hungarian Academy of Sciences, Debrecen 10, P.O.Box 7, H-4010 Hungary

E-mail:[email protected]

The recent studies of the UD team were focussed on the following topics (mtppms = meta-monosulfonated triphenylphosphine):

1. Synthesis and properties of [RuHCl(CO)(mtppms)3] 2. Water-soluble Ru(II)-N-heterocyclic carbene complexes 3. Immobilization of water-soluble complex catalysts by ion exchange 4. Characterization of the products of the reaction of [{RuCl2(mtppms)2}2]

(+ mtppms) with H2 at atmospheric and elevated pressure; classical and non-classical

hydrides 5. Computational studies on the mechanism of selective catalytic

hydrogenations in aqueous systems

6. Reactions of phenylacetylene with formic acid 7. The use of Cu(I)- mtppms complexes in aqueous organometallic catalysis

The presentation will cover topics # 1-3, while # 4 will be described in a

separate presentation by Gábor Papp, and # 6 and 7 by Wojciech Wojtków, both from the Debrecen laboratory. Most of the computational studies were carried out in collaboration with the research group of Prof. Agustí Lledós and some of the results will be presented by the Barcelona team.


12

C-7 SYNTHESIS AND USE OF NEW CHIRAL AND POTENTIALLY WATERSOLUBLE PHOSPHINES LIGANDS

FROM NATURALLY OCCURRING AMINO ACIDS Chiara Ciardi,a Luca Gonsalvi,b Maurizio Peruzzini,b Gianna Reginato,b Antonio

Romerosa,a Manuel Serrano-Ruiz a

a Universidad de Almería, Departamento de Química Inorgánica, 04120, La Cañada de San

Urbano, Almería, Spain; b CNR-ICCOM- Polo Scientifico- v. Madonna del Piano I 50119 Sesto Fiorentino, Italy

The chemistry of chiral water-soluble transition metal complexes has gained a considerable interest because of their possible applications in catalysis and biomedicine1. Due to their versatile coordination chemistry functionalized phosphines are very attractive class of ligands in this area. Here we present a simple approach to prepare a new class of γ-amino β-hidroxy phosphines which can be obtained through synthetic elaboration of naturally occurring L-amino acids. Key step of the synthetic pathway is the regioselective epoxide ring opening using the lithium salt of HPPh2(BH3)2,3.

R COOH

NHBocR

NHBoc

OR

NHBoc

OHPPh3.BH3

HPPh2(BH3)

BuLi

We synthesized and characterized new Rh(I), Ir(I) and Ru(II) carrying such new phoshine ligands whose catalytic efficiency was evaluated in different catalytic processes.

______________ References: 1. Katti K.V.; Gali H., Smith C.J.; Berming D.E. Acc. Chem. Res. 1999, 32, 9 2. Muller G., Sainz D. J. Organometallic Chem. 1995, 495, 103. 3. McNulty J., Zhou Y. Tetrahedron. Lett. 2004, 45, 407

Acknowledgements:



13

C-8- THE EFFECTS OF ELECTRIC AND MAGNETIC FIELDS ON THE 3D STRUCTURE OF BIOLOGICAL SYSTEMS IN

AQUEOUS/GEL SOLUTIONS

Abel Moreno

Instituto de Química, UNAM. Circuito Exterior, C.U. México, D.F. 04510. México. E-mail: [email protected]

In the last decade, several publications devoted to investigate the crystal growth

of model proteins like lysozyme (Mr 14,296) or thaumatin (Mr, 22,203), among others have appeared, but only few of them are based on covering all steps of the crystal growth process into two different aqueous media. This process requires not only to obtain the crystal but also to go from the over-expression, purification, crystallization, morphology of crystals up to the 3D structural analysis (assessment of crystal quality, data collection, and crystal contacts). Biological applications always require not only large enough but also high quality crystals for X-ray analysis. There are nowadays several available implemented methods to obtain crystals by either using robots or automated dispensers in the high-throughput technologies. However, in spite of these facilities there are still many proteins that do not crystallize or yield crystals of poor quality and few efforts have been done to obtain extra information about their crystallization behavior to find new alternative ways to increase their crystal quality. Then, we focused our interest in understanding the role of the strong magnetic force as one of the main physical variables that affects the crystallization process and crystal quality of the enzyme aminoacyl-tRNA synthetase (DRS-1) a key enzyme in the translation process of the chemical messages encoded by the DNA into proteins.

In this work, we have quantified and compared the effects of merging gel-growth and strong magnetic field (10 Tesla) on the outcome of the crystallization process and crystal quality of two model proteins (thaumatin and lysozyme) and DRS-1. All these experiments were conducted with a same batch of protein either in solution or in gelled media. Finally, crystals grown in gel media as well as those grown under the influence of a strong magnetic field were analyzed and compared in terms of crystal quality by X-ray diffraction.


14

C-9- WATER-SOLUBLE RU AND Rh COMPLEXES FOR SELECTIVE OXIDATIONS AND HYDROGENATIONS

Vanessa Landaeta, Maurizio Peruzzini and Luca Gonsalvi

Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti OrganoMetallici (ICCOM-

CNR). Via Madonna del Piano, 10, 50019 Sesto Fiorentino (FI), ITALY. E-mail: [email protected]

Sulfur containing compounds are among the worst contaminants present in

petroleum and derivatives. Hydrodesulfurization (HDS) process has been used in industry to remove these pollutants from refinery products, although it is not efficient in converting several recalcitrant types of compounds. Ultra-deep desulfurization of fuel oils has become an environmentally urgent subject as, by year 2006 regulations will limit the sulfur levels in fuels to less than 15 ppm [1,2]. Selective catalytic oxidation combined with extraction is one of the most promising methods for ultra – deep desulfurization [3]. A clean, recyclable protocol for this transformation could represent a highly desirable target for industrial applications in this field of research.

The catalytic oxidation of aryl thiophenes was carried out in homogeneous conditions using hydrogen peroxide (H2O2) because of its atom efficiency and environmentally friendliness. Systems able to catalyze oxidative desulfurization are known [2-4] and the use of hydrogen peroxide in stoichiometric amounts has been only recently examined [3].

Our search for the best catalytic system involved the synthesis of adequate Ru(VI) oxo complexes bearing N-based ancillary ligands. Oxidations of dibenzothiophene (DBT) and derivatives was carried out using a catalytic Ru:DBT ratio of 1:100 and stoichiometric quantity of H2O2 in acetonitrile at 75°C (6 hours), showing complete conversions and selectivity towards the desired product, dibenzothiophene sulfone (DBTSO2) which was recoved quantitatively by simple cooling of the reaction mixture after catalysis.

S SO O

DBT DBTSO2

2 H2O2

[Ru(NN)O2]

EC contribution through project MRTN-CT-2003-503864 (Aquachem) is gratefully acknowledged. ______________ References: 1. US EPA, Dec 2000; Directive EU, 2001, 11.05. 2. Murata, S.; Murata, K.; Kidena, K.; Nomura, M. Energy & Fuels, 2004, 18, 116. 3. Li, C.; Jiang, Z.; Gao, J.; Yang, Y.; Wang, S.; Tian, F.; Sun, F.; Sun, X.; Ying, P.; Han, C. Chem. Eur. J., 2004, 10, 2277. 4. Tetsuo, A. EP056532. 1993.


15

C-10- SYNTHESIS OF NEW HYDROTRIS(1-PYRAZOLYL) METHANE AND TRIS(1-PYRAZOLYL)METHANESULFONATE

COMPLEXES IN AQUEOUS MEDIUM

Luísa Martins, a,b Elisabete Alegria,a,b Telma Silva a,b,c and Armando Pombeiro b

a Departamento de Engenharia Química, ISEL, R. Conselheiro Emídio Navarro, 1950-062 Lisboa, Portugal.

b Centro de Química Estrutural, Complexo I, IST, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. c Área Científica de Física, ISEL, R. Conselheiro Emídio Navarro, 1950-062 Lisboa, Portugal.


The coordination chemistry of tris(1-pyrazolyl)methanes is a field of a current

growing interest under various viewpoints, not only for improving a fundamental knowledge (e.g,. on structural and physicochemical properties and on reactivity) but also to develop topics with an applied character such as catalysis. In fact, the anionic derivatives tris(1-pyrazolyl)methanesulfonates, which are hydrolytically stable and soluble in polar protic solvents, are particularly promising for liquid biphasic catalysis in view of the water-solubility of their transition metal complexes. However, the coordination chemistry of these N3 tripodal ligands has been reported only scarcely [1].

Here we report the synthesis and characterization, including the crystal structure and electrochemical behaviour, of new pyrazole (Hpz), hydrotris(1-pyrazolyl)methane (HCpz3) and tris(1-pyrazolyl)methanesulfonate (SO3Cpz3)- complexes of Re(III, V and VII) [2] (e.g., [ReCl2{N2C(O)Ph}(Hpz)(PPh3)2], [ReCl(X){N2C(O)Ph}(Hpz)2(PPh3)] (X = Cl or F), [ReCl2(3,5-Me2Hpz)3(PPh3)]Cl, [ReCl3{HC(3,5-R2pz)3}] (R = H or Me) [ReCl2(HCpz3)(PPh3)][BF4], [ReOCl(SO3Cpz3)(PPh3)]Cl and [ReO3(SO3Cpz3)]), Fe(II) (e.g., [FeCl2(HCpz3)]) and V(IV and V) (e.g, [VO{HC(3,5-R2pz)3}][BF4]3 (R = H or Me), [VCl3(SO3Cpz3)] and [VCl2(SO3Cpz3)(L)]Cl (L = DMF or η2-HC≡CCH2CH2OH)).

The above complexes can act as catalysts in the oxidation of ethane to acetic acid or in the peroxidative oxidation of cyclohexane to cyclohexanone and cyclohexanol, under mild conditions (at room temperature) in aqueous medium, as examples with industrial significance within the challenging field of alkane functionalization. ______________ References: 1. Bigmore H.R., Lawrence S.C., Mountford P., and Tredget C.S., Dalton Trans., 2005, 635. 2. Alegria, E.C.B.A., Martins, L.M.D.R.S., Guedes da Silva, M.F.C., Pombeiro, A.J.L., J. Organomet. Chem., 2005, 690, 1947. Acknowledgements: This work has been supported by the AQACHEM Project RTN nº MRTN-CT-2003-503864, the IPL/41/2003 project, the POCTI (FEDER funded) and the PRODEP programmes and by the Fundação para a Ciência e Tecnologia (FCT), Portugal.


16

C-11- PEROXIDATIVE OXIDATION OF CYCLOHEXANE IN AQUEOUS MEDIUM BY RHENIUM AND IRON COMPLEXES

Elisabete Alegria,a,b Luísa Martins,a,b and Armando Pombeirob

aDepartamento de Engenharia Química, ISEL, R. Conselheiro Emídio Navarro, 1950-062

Lisboa, Portugal. bCentro de Química Estrutural, Complexo I, Instituto Superior Técnico, Av. Rovisco Pais, 1049-

001 Lisboa, Portugal. E-mail: [email protected]

The oxidation of cyclohexane is an important industrial process, since some of

its products such as cyclohexanone and adipic acid are used as intermediates for Nylon manufacture. Previous studies have revealed that the main products obtained upon oxidation of cyclohexane are cyclohexanone, cyclohexanol and adipic acid. [1]A current process used in industry consists in the use of homogeneous cobalt salts, using dioxygen as oxidant at 150 ºC. This process gives cyclohexanone (85 % selectivity) with an yield of ca. 4 %. [2] Hydrogen peroxide is a convenient oxidant since it just produces water as a by-product, but the conversions and turnovers of the cyclohexane oxidation with H2O2 are usually still low.

The new hydrotris(pyrazolyl)methane and tris(pyrazolyl)methanesulfonate complexes [ReCl3(HCpz3)] and [ReO3(SO3Cpz3)], as well as related pyrazole and parent complexes, such as [ReClF{N2C(O)Ph}(Hpz)2(PPh3)] and [ReOCl3(PPh3)2], act as catalysts in the peroxidative oxidation of cyclohexane to cyclohexanone and cyclohexanol, under mild conditions (at room temperature and using an aqueous solution of H2O2), with TONs over 200.

The hydrotris(pyrazolyl)methane, tris(pyrazolyl)methanesulfonate and hydrotris(pyrazolyl)borate iron(II and III) were also tested in this catalytic process. The effects of various parameters such as the amount of catalyst, type of oxidant or of solvent, presence of a radical trap, time, oxidant-to-catalyst molar ratio and temperature are reported.

Re or Fe cat.

OH

H2O2

O

+

A comparison with the activity of other Re [3] and Fe [4] catalysts reported by us will also be provided. ______________ References: 1. K. S. Anisia, A. Kumar, Appl. Cat. A: Gen. 2004, 273, 193. 2. W. Weissermel, H. J. Horpe, Ind. Org. Chem., 2nd ed., VCH Press, Weinheim 1993. 3. Kirillov A.M., Haukka M., Guedes da Silva M. F. C. and Pombeiro A. J. L., Eur. J.Inorg. Chem., 2005, 2071. 4. M. N. Kopylovich, A. M. Kirillov, A. K. Baev, A. J. L. Pombeiro, J. Mol. Cat. A., 2003, 206, 163.

Acknowledgements:

This work has been supported by the AQUACHEM Project RTN nº MRTN-CT-2003-503864, the IPL/41/2003 project, the POCTI (FEDER funded) and the PRODEP programmes and by the Fundação para a Ciência e Tecnologia (FCT), Portugal.


17

C-12- ORGANOMETALLIC DERIVATIVES OF PHOSPHORUS DENDRIMERS

Anne-Marie Caminade, Régis Laurent, Paul Servin, Jean-Pierre Majoral

Laboratoire de Chimie de Coordination du CNRS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France. E-mail: [email protected]

Dendrimers are highly tuneable hyperbranched macromolecules, which induce an

increasing interest, with more than 1000 publications and more than 120 patents last year. This interest is mainly driven by the high number of functional groups they can bear, and by the enormous diversity of these functional groups. We synthesize since eleven years dendrimers1 possessing one phosphorus atom at each branching point,2 and we have amply studied the reactivity and functionalization of these compounds in every part of their structure (surface, branches, and core).3 This contribution will give an overview of the various types of organometallic derivatives4 of these phosphorus dendrimers we have synthesized.

= organometallic derivative= other functional group

Some uses and applications of these special dendrimers, in particular in the field of materials science5 (hybrid materials,6 modified electrodes7) and catalysis8 will be shown.

References: 1. Launay N., Caminade A.M., Lahana R., Majoral J.P. Angew. Chem. Int. Ed. Engl. 1994, 33, 1589. 2. Majoral J.P., Caminade A.M. Chem. Rev. 1999, 99, 845. 3. a) Leclaire J., Coppel Y., Caminade A.M., Majoral J.P. J. Am. Chem. Soc. 2004, 126, 2304. b) Leclaire J., Dagiral R., Fery-Forgues S., Coppel Y., Donnadieu B., Caminade A.M., Majoral J.P. J. Am. Chem. Soc. 2005, 127, 15762. 4. a) Caminade A.M., Majoral J.P. Coord. Chem. Rev. 2005, 249, 1917. b) Majoral J.P., Caminade A.M., Laurent R. ACS Symp. Series n°928 Metal-containing and metallosupramolecular polymers and materials U.S. Schubert, G.R. Newkome, I. Manners Eds, 2005, Chap. 17. 5. Caminade A.M., Majoral J.P. Accounts Chem. Res. 2004, 37, 341. 6. Boggiano M.K., Soler-Illia G.J.A.A., Rozes L., Sanchez C., Turrin C.O., Caminade A.M., Majoral J.P.

Angew. Chem. Int. Ed. 2000, 39, 4249. 7. Turrin C.O., Chiffre J., de Montauzon D., Balavoine G., Manoury E., Caminade A.M., Majoral J.P. Organometallics 2002, 21, 1891. 8. a) Koprowski M., Sebastian R.M., Maraval V., Zablocka M., Cadierno-Menendez V., Donnadieu B., Igau A., Caminade A.M., Majoral J.P. Organometallics 2002, 21, 4680. b) Laurent R., Caminade A.M., Majoral J.P. Tetrahedron Lett. 2005, 46, 6503.


18

C-13- STUDY OF CH/π INTERACTIONS IN ACETYLACETONATO COMPLEXES

Miloš K. MILČIĆ, Vesna B. MEDAKOVIĆ, Dusan N. SREDOJEVIĆ, Nenad O.

JURANIĆ and Snežana D. ZARIĆ

Department of Chemistry, University of Belgrade, Studentski trg 16, 11001 Belgrade, Serbia and Montenegro

E-mail: [email protected] The noncovalent interactions of the π-systems have been extensively studied in last years. These interactions are important for many molecular systems, from molecular biology to crystal engineering. Cationic metal complexes are involved in cation-π interactions, metal ligand aromatic cation-π (MLACπ) interactions; where ligands coordinated to the metal interact with aromatic systems.1,2 These interactions can be considered also as a type of XH/π hydrogen bonds. Strong intermolecular MLACπ interactions between cationic metal complexes and tetraphenylborate (TFB) anion were found and these are examples of some of the strongest XH/π hydrogen bonds.3 Recently it was observed that planar chelate rings with delocalized π-bonds can involve in noncovalent interactions in similar way as organic aromatic rings, indicating that these chelate rings could have aromatic character. By analysing crystal structures of metal complexes and by quantum chemical calculations it was show that chelate ring can be hydrogen atom acceptor in CH/π interactions. Geometries and energies of these interactions are similar to the CH/π interactions with organic aromatic rings.4

CH/π interactions between coordinated acetylacetonato ligand and phenyl ring were studied. By coordinating to metal atom acetylacetonato ligand makes planar chelate ring with the delocalized bonds. Acetylacetonato ligand may engage in two types of interactions; it can be hydrogen atom donor, or π-system of the chelate ring can be hydrogen atom acceptor. The interactions were analyzed in crystal structures from Cambridge Structural Database and by quantum chemical calculations. The calculated energy and the optimal distance for interactions are similar for both types of interactions; the energy is around 1.6 kcal/mol, and the distance is around 2.6 Å. Analysis of crystal structures and calculations show that interactions with acetylacetonato ligand as hydrogen atom donor depend on the metal in acetylacetonato chelate ring. The chelate rings with soft metals make stronger interactions. The same trend was not observed in the interactions where acetylacetonato chelate ring is hydrogen atom acceptor.

______________ References: 1. Zarić, S. D. Eur. J. Inorg. Chem. 2003, 2197. 2. Milčić, M. K.; Zarić, S. D.; Eur. J. Inorg. Chem. 2001, 2143. 3. Milčić, M. K.; Tomić, Z. D.; Zarić, S. D. Inorg. Chim. Acta. 2004, 357, 4327. 4. Medaković, V. B.; Milčić, M. K.; Bogdanović, G. A.; Zarić, S. D. J. Inorg. Biochem. 2004, 98, 1867.


19

C-14- COMPUTATIONAL MODELLING OF REACTION MECHANISMS IN AQUEOUS MEDIA

Agustí Lledós

Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Spain


A deeper comprehension of the reaction mechanisms of the organometallic

transformations in water is required for developing efficient catalytic processes in aqueous media. Reaction mechanisms in aqueous solution can be very different to those in the conventional organic solvents, because water does not behave as a mere solvent, but can play an active role in the reactions. Water molecules can form hydrogen bonds with different parts of the catalyst or the substrate can take part in proton transfer reactions and can coordinate to the metal centers. Moreover, the pH of the solution can alter the presence of the different catalytically active species. Computational methods can help giving a microscopic picture of the organometallic reactivity in water. In the framework of the AQUACHEM network we have started an initiative devoted to this aim. The subject of our study has been the selective C=C/C=O reduction of α,β-unsaturated aldehydes catalyzed by water-soluble Ru(II) complexes. Joó and co-workers demonstrated that ruthenium complexes with m-TPPMS ligands perform a selective reduction of the different double bonds depending on the pH of the reaction medium. In acidic solutions the product of the reaction was exclusively that formed by the saturation of the olefinic double bond, while in basic solution selective hydrogenation of the C=O bond takes place.1 Despite the experimental determination of the starting active species as a function of the pH, the mechanistic features of the reaction have remained unknown. Moreover, the origin of the selectivity in the hydrogenation has not been explained yet. Both questions have been addressed in the computational study. The results related to the acidic medium2 will be presented in the lecture.

_____________ References: 1. (a) Joó, F.; Kovács, J.; Bényei, A. C.; Kathó Á. Angew. Chem. 1998, 110, 1024. (b) Joó, F.; Kovács, J.; Bényei, A. C.; Kathó Á. Catal. Today 1998, 42, 441.. 2. Kovács, G.; Ujaque, G.; Lledós, A.; Joó, F. Organometallics, submitted.


20

C-15- POLY(DIMETHYLSILOXANE) CHAINS AS SOLUBILISERS OF CuCOMPLEXES IN SUPERCRITICAL CARBON DIOXIDE

Matthew Herbert, Francisco Montilla, Antonio Pastor, Agustín Galindo

Dpto. Química Inorgánica. Fac. Química. Universidad de Sevilla. 41071 Sevilla, Spain.

E-mail: [email protected] Supercritical carbon dioxide (scCO2) is a relatively green alternative to commonly used organic solvents and research into its use as a reaction solvent is therefore desirable.1 Although metal catalysed homogeneous reactions in scCO2 would be attractive, the low solubility of many catalysts usually presents a problem. Recent research has therefore looked at enhancing the solubility of such catalysts in the supercritical medium. In previous work we have successfully used TMS groups2 and carbosilane dendrons3 attached to ligands to address this problem. Here we report a new approach for improving the solubility of metal complexes in scCO2 by the functionalisation of their ligands with poly(dimethylsiloxane) chains. Rayner, Kerton et al. have recently used this strategy to solubilise poly(dimethylsiloxane)-derived phosphine and phosphinite complexes.4 The attachment of polydimethylsiloxane chains onto a pyridine ligand was achieved through hydrosilylation of 4-vinylpyridine with hydride terminated polydimethylsiloxane. The resulting pyridine-tagged ligand was identified to be a mixture of the isomers resulting from the Markovnikoff and anti-Markovnikoff addition. Reaction of this ligand with [Cu(AcO)2(H2O)]2 in ethanol yielded a green oil, which was identified as a copper acetate complex containing the typical dimeric Cu2(OAc)4 core, and with a copper content of 4-6 % by weight. The effectiveness of polydimethylsiloxane chains as solubilising groups was demonstrated through solubility studies of the copper compound in scCO2. Whereas the latter compound showed a solubility ca. 1.7 mM [Cu] in scCO2, no detectable solubility was observed for the related copper acetate derivatives.

Cu

OO

NN

OO

OO

Cu

OO

C2H4-SiMe2(OSiMe2)n(Me2SiO)n SiMe2-C2H4

m Preliminary results obtained in the selective oxidation of nitrobenzyl alcohol, using the Cu complex in combination with TEMPO as co-catalyst and O2 as terminal oxidant, in scCO2, are discussed.. Complete conversion to the aldehyde was observed after 4 hours of reaction at 60 ºC and 150 bars.

O2N

CH2OH

[Cu]/TEMPO/O2

scCO2

O2N

CHO

References: 1. (a) Jessop, P. G.; Leitner, W. in Chemical Synthesis Using Supercritical fluids, Wiley-VCH, 1999. (b) Special issue devoted to supercritical fluids: Chem. Rev., 1999, 99(2). 2. Montilla, F.; Galindo, A.; Rosa, V.; Avilés, T. Dalton Trans., 2004, 2588. 3. Montilla, F.; Galindo, A.; Andrés, R.; Córdoba, M.; de Jesús, E.; Bo, C. Manuscript in preparation. 4. Saffarzadeh-Matin, S.; Chuck, C. J.; Kerton, F. M.; Rayner, C. M. Organometallics, 2004, 23, 5176.


21

C-16- ACTIVATION OF PEROXIDES BY HEME AND NON-HEME Fe(III) COMPLEXES

Ariane Brausam, Maria Wolak, Alexander Theodoridis and Rudi van Eldik*

Institute for Inorganic Chemistry, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058

Erlangen, Germany.

One important step in the activation of oxygen by both non-heme and heme enzymes is formation of a Fe-peroxo species accompanied by subsequent cleavage of the O-O bond to give a high valent Fe-oxo species. To gain insight into the mechanism of the reaction, two model complexes for both types of enzymes were chosen. Stopped-flow and high pressure techniques were applied to investigate the reaction of these complexes with various peroxides at different pH values.

Non-heme FeIII(TAML) complexes are long lived, oxidation robust and water soluble catalysts for oxidation reactions. The reaction of FeIII(TAML) complexes with H2O2 was observed within a pH range of 7.7 – 11.5. During this reaction a brown intermediate is formed. The formation reaction is a two step process. Both steps were investigated separately. The first step shows a sigmoidal pH dependence for k1, from which the pKa value for the deprotonation of one of the axial aqua ligands of the employed complex can be determined. Due to the labilizing trans-effect of the OH group, the (H2O)(OH)FeIII(TAML) complex shows a higher reactivity than the diaqua complex. The hydrogen peroxide concentration dependence of k1 in the first step reaches saturation over the whole investigated pH range. Because of the higher reactivity of the (H2O)(OH) FeIII(TAML) complex, kinetic saturation is reached at much lower concentrations of H2O2 at higher pH values. Activation parameters (∆S≠, ∆H≠, ∆V≠) are presented for two different pH values. For the second step of the reaction, a bell-shaped pH dependence was found. pH profiles for H2O2 activating enzymes are usually bell-shaped, which indicates that the reactive intermediate responsible for the oxidation reactions is formed during the second step of the reaction. Activation parameters (∆S≠, ∆H≠, ∆V≠) are presented again for two different pH values. A mechanism that accounts for the observed will be presented.

FeIII(TMPS) was selected as a representative heme-Fe(III) complex. Rate constants and activation parameters ∆S≠, ∆H≠ and ∆V≠

were determined for the reaction with H2O2 and cumene hydroperoxide in the pH range of 2 to 13. The observed rate constant kobs describes a two-step process, where kobs is kK. The equilibrium assigned to K is assumed to be the coordination of peroxide followed by cleavage of the O-O bond to give a high valent Fe-species. The observed rate constants and activation parameters reflect the energetics, volume and entropy changes involved in both the initial equilibrium K and the subsequent redox step k. The relative contributions of these two reaction steps to the observed kinetics depend on pH and the nature (structure and redox properties) of the oxidant. The trends observed in the values of ∆V≠ for the reaction of both oxidants as a function of pH can in a first approximation be correlated with the volume changes expected for the binding of ROOH to FeIII(TMPS) and the subsequent cleavage of the O-O bond.


22

C-17- BORYLATION: MECHANISTIC STUDIES AND LINKS TO C-F BOND ACTIVATION

Robin N. Perutz,a Marius V. Câmpian,a Richard J. Lindupa and Todd B. Marderb

a Department of Chemistry, University of York, York YO10 5DD, UK

b Department of Chemistry, University of Durham, Durham DH 1 3LE, UK

Photo-induced dissociation of ligands from metal complexes can lead to oxidative addition of CH, or Si H bonds in added substrates. We have recently used this methodology to observe BH and BB oxidative addition at ruthenium and rhodium complexes. These experiments provide mechanistic information about the individual steps involved in borylation of arenes and alkanes, a recently discovered catalytic process of great importance. Our experiments fall into two groups. In the first we have employed dihydride complexes such as Ru(depe)2H2 (depe = Et2PCH2CH2PEt2) as precursors and have used multinuclear NMR spectroscopy to identify the products of BH oxidative addition. We have employed laser flash photolysis to measure the rate of oxidative addition of BH bonds (Scheme 1) [1]. In the second group of experiments, we have studied the photochemistry of half-sandwich complexes such as (�5-C5H5)Rh(PPh3)(C2H4) by NMR spectroscopy and have adopted competition methods to compare the rates of oxidative addition of BH bonds with B B, CH and Si H bonds.

Ru

R2PR2P H

B

PR2

PR2

O

O-H2

R = Et

HBpin

kobs = 107 dm3 mol−1

s−1

hνRu(depe)2H2 Ru(depe)2

kobs

HBpin = BO

OH

Scheme 1 H-H reductive elimination followed by B-H oxidative addition

We have also examined borylation via C-F bond activation. We showed that Rh(PMe3)3(SiPh3) reacts with polyfluorinated pyridines to form Rh(PMe3)3(ArF) (Scheme 2). Subsequent reaction with excess B2(cat)2 successfully formed Rh(PMe3){B(cat)}3 and the fluorinated boryl derivatives ArFB(cat) (cat = catecholate) in quantitative yield. These reactions constitute the first demonstration of borylation via C-F bond activation. They also provide direct evidence for the conversion of metal aryls to arylboronates.

RhMe3P

PMe3

PMe3

SiPh3 N

FF

F F

F

RhMe3P

Bcat

PMe3

BcatcatB

PMe3

Rh

PMe3

Me3P PMe3

N F

FF

F

N

F

F

FF

Bcat

Rh

PMe3

Me3P PMe3

N

F

F

FF

+room temp

+

B2(cat)2+

- FSiPh3

N F

FF

F

Bcat

+

Scheme 2. Borylation via rhodium-mediated C-F bond activation

_____________ References:

1. P L Callaghan, R Fernandez-Pacheco, N Jasim, S Lachaize, T B Marder, R N Perutz, E Rivalta and S Sabo-Etienne, Chem. Comm., 2004, 242-243.

Acknowledgments: We acknowledge the support of EPSRC and the European Union.


23

C-18- CHEMISTRY IN AQUEOUS MEDIUM AT THE IST GROUP: AN OVERALL VIEW

Armando J.L. Pombeiro

Centro de Química Estrutural, Complexo I, Instituto Superior Técnico,

Av. Rovisco Pais, 1049-001 Lisboa, Portugal E-mail: [email protected]

During the second year of the AQUACHEM project, the studies of the IST group

were mainly directed towards the following areas: - Self-assembly syntheses of water soluble mono-, di-, tri- and polynuclear

copper(II) complexes with N,O-ligands and aromatic carboxylates, and their applications as catalysts for the peroxidative oxidation of alkanes, in aqueous medium and under mild conditions, thus partially mimicking particulate methane monooxygenase.

The possibility of extension of the catalytic activity to olefins hydrogenation was also demonstrated by preliminary experiments in cooperation between the IST and the UD (Prof. Ferenc Joo) teams.

- Syntheses of metal complexes with water soluble tris(pyrazolyl)methanesulfonate and related scorpionate ligands and their application as catalysts for the peroxidative oxidation of cyclohexane by aqueous hydrogen peroxide, at room temperature.

- Syntheses of rhenium complexes with N,O-ligands related to Amavadine models and their use, as well as of other more easily available metal compounds, as catalysts for functionalization reactions of alkanes under mild conditions.

- Syntheses of platinum complexes with water soluble phosphines. - Electrochemical investigation of water soluble azole-ruthenium complexes with

anti-tumor activity. These studies are outlined and their significance from synthetic, catalytic,

biological and/or pharmacological viewpoints is discussed.

______________ References: 1. E. Reisner, V.B. Arion, A. Eichinger, N. Kandler, G. Geister, A.J.L. Pombeiro and B.K. Keppler, “Tuning of Redox Properties for the Design of Ruthenium Anticancer Drugs: Part 2. Syntheses, Crystal Structures and Electrochemistry of Potentially Antitumor [RuIII/IICl6-n(azole)n]z (n = 3,4,6) Complexes”, Inorg. Chem., 2005, 44, 6704-6716. 2. A.M. Kirillov, M.N. Kopylovich, M.V. Kirillova, M. Haukka, M.F.C. Guedes da Silva and A.J.L. Pombeiro, “Multinuclear Copper Triethanolamine Complexes as Selective Catalysts for the Peroxidative Oxidation of Alkanes under Mild Conditions”, Angew. Chem., Int. Ed., 2005, 44, 4345-4349. 3. A.M. Kirillov, M. Haukka, M.F.C. Guedes da Silva e A.J.L. Pombeiro,“Preparation and Crystal Structures of Benzoylhydrazido- and –diazenidorhenium Complexes with N,O-Ligands and Their Catalytic Activity towards Peroxidative Oxidation of Cycloalkanes”, Eur. J. Inorg. Chem., 2005, 2071-2080. 4. A.M. Kirillov, M.N. Kopylovich, M.V. Kirillova, E. Yu. Karabach, M. Haukka, M.F.C. Guedes da Silva, A.J.L. Pombeiro, “Mild peroxidative oxidation of cyclohexane polynuclear copper triethanolamina complexes”, Adv. Synth. Cat., submitted for publication.

Acknowledgements:

This work has been supported by the European AQUACHEM project MRTN-CT-2003-503864, the Fundação para a Ciência e a Tecnologia, Portugal, and its POCTI (FEDER funded) programme.


24

C-19- SPECTROSCOPIC AND THEORETICAL STUDIES OF THE SOLVENT INFLUENCE ON THE PROTON TRANSFER TO

TRANSITION METAL HYDRIDES

E. Shubina, N. Belkova

The current knowledge on the aqueous behavior of organometallic compounds in general and hydride compounds in particular is still rather limited. Acidity and basicity scales change on going from the gas phase (or apolar organic solvents) to a protic solvent such as water in ways that are still not completely understood. The influence of the solvent properties (polarity and ability to form hydrogen bonds) on proton transfer to and from metal hydrides has not been previously investigated. To address these questions tThe dihydrogen bonding and proton transfer from substituted phenols to the ruthenium dihydride complex [P(CH2CH2PPh2)3]RuH2 was studied in dichloromethane, THF and in THF/H2O, THF/CH3OH and THF/CH3CN mixtures, showing the influence of solvent polarity and/or proton donor/proton acceptor properties on the position of the proton transfer equilibrium. Formation of ion pairs stabilized by the hydrogen bond between the non-classical cation [RuH(η2H2)]+ and homoconjugated anion [ArOHOAr]- was determined in low-polar media. The increase of the media polarity favors proton transfer but leads to the dissociation of hydrogen bonded ion pairs [RuH(η2H2)]+…[ArOHOAr]-. Under comparable media polarity presence of protic solvent in the mixture favors proton transfer at higher extent due to the additional H-bonding with solutes. The structural, energetic and electronic features of the dihydrogen bonded adducts and of proton transfer were investigated by means of DFT/B3LYP calculations of the model dihydride [P(CH2CH2PH2)3]RuH2 and different proton donors. The specific and non-specific influence of the media properties on the dihydrogen bonding and proton transfer was studied by PCM calculations or by introducing the second proton donor or solvent molecule in the model system. The additional participation of external molecules, either from the solvent or the alcohol, strengthens remarkably the dihydrogen bonded adducts and eases the proton transfer process.


25

C-20- NEW FERROCENYL LIGANDS FOR (ASYMMETRIC) CATALYSIS: CANDIDATES FOR CATALYSIS IN AQUEOUS

MEDIA?

Eric Manoury, Agnès Labande, Raluca Malacea, Lucie Routaboul, Joffrey Wolf, Jean-Claude Daran, Rinaldo Poli

Laboratoire de Chimie de Coordination, CNRS UPR 8241 (liée par convention à l’Université Paul Sabatier et l’Institut National Polytechnique), 205 route de Narbonne, 31077 Toulouse

Cedex 4

Catalysis in aqueous media, which allows a limited use of harmful organic

solvents, has become an economical and environmental challenge in research. Our group is now involved in the development of “green” processes in chemistry. The establishment of general methods for the synthesis of polysubstituted ferrocenes with various substitution patterns1,2 has given us access to a wide range of bi-3 or tridentate ligands.4 ,5,6Most of them can be prepared in an enantiomerically pure form.

CH2OH

PPh2SCH2SR

PPh2S

CH2SR

PPh2

CHO

PPh2S

O

(CH2)nO

R2

R4R3

R1

n= 0 ou 1PPh2

CH2

PPh2

N NR

+

Fe

Fe Fe

Fe Fe

Fe

The coordination chemistry of these ligands has been studied with various

metals (Pd, Pt, Rh, Ir, Ru...) and the resulting complexes have been tested successfully in several catalytic reactions (allylic alkylation, hydrogenation, C-C bond formation), especially asymmetric catalytic reactions.

References: 1. Iftime, G., Daran, J.-C., Manoury, E., Balavoine, G. G. A., Angew. Chem. Int. Ed., 1998, 37, 1698-1701. 2. Chiffre, J., Coppel, Y., Balavoine, G. G. A., Daran, J.-C., Manoury, E., Organometallics, 2002, 21, 4552-4555. 3. Wolf, J. ; Labande, A. ; Daran, J.-C. ; Poli, R. J. Organomet. Chem. 2005, in press. 4. Chiffre, J., Coppel, Y., Balavoine, G. G. A., Daran, J.-C., Manoury, E., Organometallics, 2002, 21, 4552-4555. 5. Routaboul, L., Vincendeau, S., Daran, J.-C., Manoury, E., 2005, 16, 2685-2690. 6. Mateus, N., Routaboul, L., Daran, J.-C., Manoury, E, J. Organomet. Chem., 2005, in press.


26

PPh2

CH2Rh

S CO

Cl

Ph

Fe

Ph2P

Fe

NN R

RhBF4

We now plan to extend the range of ligands by adding supplementary functions in order to make them hydrosoluble and so to allow the development of catalytic processes in aqueous media.


27

C-21- THE CIESOL A RESARCH CENTRE TO FIND NEW APPLICATIONS FOR THE SUN

Amadeo Fernández

Área de Química Analítca. Universidad de Almería. Cañada San Urbano s/n 04120

CIESOL

Centro de Investigaciones

Research Center on


28

C-22- ORGANOMETALLIC CATALYSIS IN AQUEOUS MEDIA THE USE OF DENDRITIC PTA LIGANDS

P. Servin, R. Laurent, A.-M. Caminade, J.-P. Majoral

Laboratoire de Chimie de Coordination du CNRS, 205 route de Narbonne, 31077 Toulouse Cedex 4

E-mail : [email protected]

Recently PTA (1,3,5-triaza-7-phosphaadamantane)1 has received increased attention not only because of its ability to stabilize low metal oxidation states but also due to that it is water-soluble.2 These characteristics make it an excellent ligand for a water-soluble catalytical metal complex.

This work is part of a project funded by the European Community* which goal is to make reactions and catalysis in water due to its low toxicity and cost. By grafting a catalyst to a phosphorous-containing dendrimer the metal leaching may be diminished and the catalyst recovery may be increased.3 Catalytical selectivity may also occur due to the size of the ligand as well as the local high density of catalyst on the surface.

We have therefore synthesized several generations of water-soluble phosphorous-containing dendrimers with PTA on the surface. Attempts were made to react these with different metal complexes until we finally succeeded to make dendritic catalysts with [(p-cymene)RuCl2]2.

N3P3 ON N

MePS

ON+

NN

P

Cl-

Ru

p-cymene

ClCl

6 2

NN

N

P

RuClCl

p-cymene

Non-alkylated Monomer Chemical structure of the 1st dendrimer generation

MeON+

NN

P

RuClCl

p-cymene

Cl-

1st generation 2nd generation 3rd generation

N+

NN

P

RuClCl

p-cymene

Cl-

12G'

c1

N+

NN

P

RuClCl

p-cymene

Cl-

24G'

c2

N+

NN

PRu

ClCl

p-cymene

Cl-

48G'

c3

Dendrimers

In the field of alcohol isomerization4 some preliminary results have been achieved. ______________ References: 1. D. J. Daigle, Inorg. Synth., 1998, 42, 40-45 2. A. D. Phillips, L. Gonsalvi, A. Romerosa, F. Vizza, M. Peruzzini, Coord. Chem. Rev., 2004, 248, 955-

993 3. V. Maraval, R. Laurent, A.M. Caminade, J.P. Majoral, Organometallics 2000, 19, 4025 4. V. Cadierno, P. Crochet, S. E. Garcia-Garrido, J. Gimeno, Dalton Trans., 2004, 3635-3641 * EC-AQUACHEM program, contract MRTN-CT-2003-503864


29

C-23- REACTIONS OF HEMIMETALLOCENIC MOLYBDENUM (VI) COMPLEXES WITH SULFUR COMPOUNDS

Chiara Dinoi,a Rinaldo Poli,a Jean-Claude Daran,a Miguel Baya,a

Funda Demirhan,b GülnurTabanb

a Laboratoire de Chimie de Coordination, UPR CNRS 8241, 205 Route de Narbonne, 31077

Toulouse cedex, France, [email protected] b Celal Bayar University, Faculty of Sciences & Liberal Arts, Department of Chemistry, 45030,

Muradiye-Manisa, Turkey

High oxidation organometallic compounds, mostly supported by oxo ligands, are now a well established family and exhibit remarkable catalytic activities in oxidation processes. Our group studies the chemistry of high oxidation state organometallic compounds with the long term goal of developing catalytic and electrocatalytic applications in water, the greenest available solvent. The preferred precursor has been the Cp*2Mo2O5 complex, obtained according to the synthetic procedure reported in the literature.1

The first stage of the project has been a fundamental understanding of the physical behaviour and the chemical reactivity of the Cp*MoVI system in water. Kinetic investigations of proton transfer in the entire pH range showed the stability, at low pH, of a new species Cp*MoO2

+ and the existence, in equilibrium, of the complex Cp*MoO2(OH) in the intermediate pH range 2. By chemical reduction with Zn in an acidic aqueous medium, novel oxo-supported complexes Cp*2Mo2O2(O2CCH3)2 and [Cp*3Mo3O4(O2CCF3)3]+ have been isolated and characterized.3,4

We now report on the reactivity of the Cp*2Mo2O5 complex with sulfur compounds and its extension to the well known Cp2Mo2O5 analogue.5 Compound Cp*2Mo2O5 reacts with thioglycolic acid, HSCH2COOH, to yield compound Cp*2Mo2(µ-SCH2CO2)2(µ-S), characterized by X-ray analysis (see Figure). In this reaction, the thioglycolic acid reacts as a reducing agent, as a ligand and as a substrate for C-S bond reduction.

We are grateful to the bilateral CNRS-TUBITAK program for his financial

support. ______________ References:

1. D.Saurenz, F. Demirhan, P. Richard, R. Poli, H Sitzmann, Eur. J. Inorg. Chem., 2002, 1415-1424. 2. E. Collange, J. Garcia, R. Poli, New J. Chem. 2002, 26, 1249-1256. 3. F. Demirhan, P. Richard, R. Poli, Inorg. Chim. Acta 2003, 347, 61-66. 4. F. Demirhan, J. Gun, O. Lev, A. Modestov, R. Poli, P. Richard, J. Chem. Soc, Dalton Trans. 2002,

2109-2111. . M. Cousins, M. L. H. Green, J. Chem. Soc. (A), 1969, 16-19.
5


30

C-24- NEW REACTIONS CATALYSED BY Ru(II)- AND Cu(I)-PHOSPHINE COMPLEXES IN AQUEOUS SYSTEMS

REACTIONS OF ALKYNES IN FORMICA ACID

Wojciech Wojtków

Institute of Phisical Chemistry, University of Debrecen and Research Group of Homogeneous Catalysis of the Hungarian Academy of Sciences, Debrecen 10, P.O.Box 7,

H-4010 Hungary

1. It is known from earlier studies of the Debrecen laboratory that the hydrogenation of aqueous suspensions of CaCO3 under CO2 + H2 atmosphere yields also free HCOOH in addition to Ca-formate [1]. Therefore we made model studies on the reaction of phenylacetylene with HCOOH in the presence of excess mtppms (mtppms = meta-monosulfonatedtriphenylphosphine). Phenylacetylene is known to react with HCOOH in the absence of transition metal catalyst and the main product of this reaction is acetophenone [2]. We have found that the above Ru(II)-catalyst did not accelerate the reaction, and only in a few cases were products, other than acetophenone, observed in very small quantities. The most interesting of these is cinnamic acid which may be formed by the direct anti-Markownikow addition of HCOOH across the alkyne triple bond.

2. [HCu(PPh3)6] (Stryker’s reagent) is a useful catalyst for the hydrogenation of various C=C and C=O bonds [3]. Furthermore, the Cu6H6 copper hydride can be obtained from aqueous solutions of CuSO4 by reduction with Na-hypophosphite. In pursue of a water-soluble analog of Srtyker’s reagent we prepared a Cu(I)-phosphine complex with mtppms, in an analogous way to the preparation of Na5[Cu(mtppts)2]·n H2O (mtppts = meta-trisulfonated triphenylphosphine) [4]. Catalytic properties of this compound were investigated in the hydrogenation of benzylidene acetone. The reactions yield all three possible products of C=C and C=O hydrogenation, with the preference for the saturated ketone.

______________ References: 1. I. Jószai, F. Joó, J. Mol. Catal. A: Chemical, 2004, 224, 87-91. 2. M. Rotem, I. Goldberg, U. Shmueli, Y. Shvo, J. Organometallic Chem., 1986, 314, 183. 3. J-X. Chen, J. F. Daeuble, D. Berestensky, J. M. Stryker, Tetrahedron, 2000, 56, 2153. 4. F. Tisato, F. Refosco, G. Bandoli, G. Pilloni, B. Corain, Inorg. Chem., 2001, 40 (6), 1394.


31

C-25- ON-LINE ELECTROCHEMISTRY/ESI-MS STUDIES OF TRANSITION METAL COMPLEXES

Petr V. Prikhodchenko,Vitaly Gutkin, Jenny Gun, and Ovadia Lev

Casali Institute of Applied Chemistry, Department of Chemistry, The Hebrew University of

Jerusalem, Jerusalem 91904, Israel. E-mail: [email protected]

Electrospray mass spectrometry has been increasingly used to study the

coordination of organometallic complexes. Sequential ion fragmentations by collision induced dissociation provide valuable information on the gas phase degradation pathway and the relative stability of the different residues, in addition to being a valuable structure identification tool. On line, tandem electrochemistry and electrospray mass spectrometry (EC/ESI-MS) is of particular importance due to the possibility of charge transfer induced ligand exchange because they can be used to detect charge transfer induced coordination changes. Here we describe one test case application of this method.

Halogen complexes of Ruthenium cyclopentadienyl PTA [RuCpX(PTA)2] ; [RuCpX(PTA)PPh3]; and [RuCp(mPTA)PPh3X]+ (Cp = C5H5; X = Cl-, I-; PTA = 1,3,5-triaza-7-phosphaadamantane; mPTA = [methyl,1,3,5-triaza-7-phosphaadamantane]+ synthesized by the groups of the University of Almeria, Spain and ICCOM CNR, Florence, Italy) were investigated by electrospray mass spectrometry, cyclic voltammetry and by combined, on-line electrochemistry and ESI-MS. The electrochemistry and ESI mass spectrometry of these ruthenium complexes were never described before.

The structures of the initial compounds and the products of their electrooxidation were supported by in-situ ion fragmentations (MSn) experiments with the determination of their fragmentation pathway by collision induced dissociation (CID). ESI-MS fragmentation is explained by soft acid hard base (SAHB) considerations of Ru(II) vs. Ru(III) centers. Electrochemical oxidation of the Ru(II) complexes in DMF revealed reversible single - electron oxidation. The RuII/III formal potentials of the complexes were determined by cyclic voltammetry. EC/ESI-MS, a radial electrochemical flow cell coupled directly to an ESI-MS, was used to characterize the electrooxidation products of the Ruthenium complexes.

Appearance of the different products in the MS spectra after oxidation, and the absence of the expected RuIII species can be attributed to disproportionation reactions in the MS inlet. The oxidation gives the less stable RuIII complexes which undergo slow coordination change. The RuIII complex undergoes disproportionation in the MS interface which is manifested in increased abundance of RuII species and occurrence of RuIV product.


32

C-26- SELECTIVITY OF C=O HYDROGENATION OF α,β-UNSATURED ALDEHYDES IN BASIC MEDIUM WITH RU(II)

WATER-SOLUBLE COMPLEXES: A COMPUTATIONAL ANALYSIS

Andrea Rossin, Gabor Kovács, Gregori Ujaque, Agustí Lledós, Ferenc Joó

Universitat Autònoma de Barcelona – Edifici C - Unitat Química Física, 08193 – Bellaterra

(Barcelona) – Spain. E-mail: [email protected]

Here results of a DFT study of the selective hydrogenation of cynnamaldehyde to cynnamyl alcohol performed by ruthenium(II) m-TPPMS complexes (m-TPPMS= sodium salt of triphenylphosphine meta-monosulphonato) are presented. Experimental evidence1 from NMR and potentiometric data reveals that different species are activating different functional groups, depending on the pH of the water layer. The whole mechanism being unknown, the theoretical investigation was used to cast light on the nature of the intermediates and also to explain the observed regioselectivity. In particular, the basic pH case was taken into account. The model complexes (H)2Ru(PH3)x (x=3,4. See Figure I) were reacted with propenal, and reaction profiles were developed for several alternative pathways. The solvent is introduced both by continuum (CPCM) and by discrete modeling; in the latter case a cluster made of three water units (H2O)3 was added to the metal-organic part. It is the best compromise between a realistic model and a short computational time.

(a) (b)

(c)

Figure I – Model system used to study the reaction: cis-(H)2Ru(PH3)3 (a), cis-(H)2Ru(PH3)4 (b) and acrylaldehyde [CHO-CH=CH2, (c)]..

______________ References: 1. Joó F., Kovács J., Bényei A. Cs., Kathó Á., Cat. Today 42 (1998), 441; Joó F., Kovács J., Bényei A. Cs., Kathó Á., Angew. Chem. Int. Ed. 1998, 37, 969.


33

C-27- THE EXCITED DYNAMICS OF MOLYBDATE SENSORS AND THE STRUCTURE OF THE MOLYDATE-RHENIUM SENSOR

COMPLEX

Nicole Reddig, Anne-K. Duhme-Klair, Simon B. Duckett, Robin N. Perutz

Department of Chemistry, University of York, Heslington, York YO10 5DD, UK

Monitoring of oxometalate ions such as molybdate is a developing research field for environmental, biochemical and medical concerns. As oxometalates are typically formed by high oxidation state metal ions in aqueous media, a selective analytical technique is required. Promising approaches to molybdate detection include catalytic fluorometric methods and quenching of the luminescence of organic ligands by MoVI.

Figure: Cation in 1 (left) and ball and stick model of 2 (right)

The sensor [ReI(CO)3(bpy)L1]PF6 (1) (L1 = 2,3-dihydroxyphenol-N-pyridylamide) is selective for molybdate with two sensor molecules coordinating per molybdate.1 This has been shown by luminescence titration and we have now isolated the trinuclear ReO2MoO2Re complex (2) and determined its structure (Fig.). Binding of the analyte is indicated by efficient quenching of the (Re-bpy)-based luminescence.

In order to understand the electronic processes occurring upon excitation we investigated pH-dependent time-resolved IR spectra of the sensor itself as well as the sensor in the presence of the analyte.

In addition to the presentation of the synthesis and luminescent properties of 1, a mechanism for the quenching process based on the time-resolved measurements and DFT-calculations will be proposed.

We gratefully acknowledge the contributions of A. Vlček Jr. and M. Towrie at the Rutherford Appleton Laboratory and the EC through RTN no. MRTN-CT2003-503864 (AQUACHEM) for financial support. ______________ References:

NRe+

N

N

NHO

OH

OH

CO

CO

CO

1. Peacock, F. A., Batey, H. D., Raendler, C., Whitwood, A. C., Perutz, R. N., Duhme-Klair, A.-K. Angew. Chem. Int. Ed. 2005, 44, 1712.


34

C-28- COMPARATIVE STUDY OF THE INTERACTION OF NO WITH WATER SOLUBLE CATIONIC- AND ANIONIC FeIII

PORPHYRINS

Joo-Eun Jee, Maria Wolak, Achim Zahl and Rudi van Eldik

Institute for Inorganic Chemistry, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany. [email protected]

The water soluble non µ-oxo dimer forming iron(III) porphyrin [5,10,15,20-

tetrakis-(4’-t-butyl-2’,6’-bis(4-t-butylpyridine)-phenyl)porphinato]iron(III), (P8+)FeIII, bearing eight positively-charged meso substituents and [54,104,154,204-tetra-t-butyl-52,56,152,156-tetrakis-(2,2-bis-carboxylato-ethyl)-5,10,15,20-tetraphenylporphyrin] iron (III), (P8-)FeIII, with eight negatively-charged meso substituents were characterized by UV-vis, 1H-NMR, and 17O-NMR water exchange studies in aqueous solution. The reactivity of (P8+)FeIII and (P8-)FeIII toward NO was studied as a function of pH, temperature and pressure to assess the influence of highly charged meso substituents and the nature of axial ligands on the properties of the FeIII center.1,2 The porphyrin complexes react with nitric oxide to yield the nitrosyl adducts, (Pn)FeII(NO+)(L) (L = H2O or OH-), (n = 8+, 8-). The diaqua-ligated porphyrins (Pn)FeIII(H2O)2 bind and release NO according to a dissociatively activated mechanism analogous to that reported earlier for other (P)FeIII(H2O)2 species. 2-4 Coordination of NO to (Pn)FeIII(OH) present in the solution at high pH follows an associative mode, as evidenced by negative ∆S‡

on and ∆V‡on values measured for this reaction. The observed ca 10-fold decrease in

the NO binding rate on going from six-coordinate (Pn)FeIII(H2O)2 to five-coordinate (Pn)FeIII(OH) is ascribed to the different nature of the rate-limiting step for NO binding at low and high pH, respectively.

The results obtained for (P8+)FeIII and (P8-)FeIII are compared with data reported for other water-soluble iron(III) porphyrins with positively- and negatively-charged meso substituents. 3-5

______________ References: 1. Jee, J-E, Balbinot, D.; Jux, N.; Zahl, A.; van Eldik, R. Inorg. Chem. in press. 2. Jee, J-E, Eigler, S.; Hampel, F.; Jux, N.; Wolak, M.; Zahl, A.; Stochel, G.; van Eldik, R. Inorg. Chem. 2005, 44, 7177. 3. Theodoridis, A.; van Eldik, R. J. Mol. Catal. A. 2004, 224, 197. 4. Laverman, L. E.; Ford, P. C. J. Am. Chem. Soc. 2001, 123, 11614. 5. Wolak, M.; van Eldik, R. J. Am. Chem. Soc. 2005, 127, 1331.


35

C-29- NEW 1D AND 2D WATER-SOLUBLE Cu(II) POLYMERS DERIVED FROM PYROMELLITIC ACID

Yauhen Yu. Karabach,a M. Fatima C. G. da Silva,a Matti Haukka,b

Alexander M. Kirillov,a Maximilian N. Kopylovich,a Armando J. L. Pombeiroa

a Centro de Quimica Estrutural, Complexo I, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001 Lisbon, Portugal; E-mail: [email protected], [email protected]

b University of Joensuu, Department of Chemistry, P.O. 111, FIN-80101, Joensuu, Finland;

Transition metal aqua complexes are primary species formed upon dissolution of metal salts in water. Their further hydrolytic transformations into polymeric architectures are dependent mainly on the presence of chelating and stabilizing ligands, order of addition of reagents and pH of solution. Thus, by combining copper(II) nitrate, triethanolamine (chelator), aromatic carboxylic acid (stabilizer) and sodium hydroxide in water solution we have recently developed1,2 a self-assembly synthesis of multinuclear Cu complexes and found1−3 their high catalytic potential towards peroxidative oxidation of alkanes.

In pursuit of these studies, we report herein the easy synthesis in aqueous media of new water-soluble 1D and 2D coordination polymers derived from building blocks based on mono- and dinuclear copper triethanolaminate species or copper aqua complexes, and linear-type spacers like molecules of pyromellitic acid (benzene-1,2,4,5-tetracarboxylic acid). A crucial role on the formation of the polynuclear architectures is played by the nature and order of addition of the alkali used to adjust the pH of the reaction mixture, i.e. aqueous solutions of Li+, Na+, K+ or Cs+ hydroxides lead to diverse polymeric coordination networks. The compounds obtained have been characterized by IR-spectroscopy, elemental and X-ray diffraction structural analyses, the latter establishing the 1D or 2D character of the polymeric architectures. All their OH and COO(H) groups, as well as coordinated and free H2O molecules, are further linked by O−H...O hydrogen-bonds, leading to multiple parallel chains in neighbouring layers and thus forming a 3D infinite network.

The obtained compounds act as active catalysts/catalyst precursors for liquid biphasic (H2O/MeCN) oxidation of cyclohexane, via radical mechanisms, by aqueous hydrogen peroxide at room temperature, to a mixture of cyclohexanol and cyclohexanone. The effects on the yields and TONs of various factors such as alkane, peroxide and catalyst concentrations, solvent amount and catalyst recycling, are reported.

This work has been partially supported by the Human Resources and Mobility

Marie Curie Research Training Network (AQUACHEM project, CMTN-CT-2003-503864) and the Foundation for Science and Technology (FCT), grants BD/23337/05, BD/6287/01 and BPD/14465/03, and its POCTI programme (FEDER funded). ______________ References: 1.Kirillov, A. M.; Kopylovich, M. N.; Kirillova, M. V.; Haukka, M.; da Silva, M. F. C. G.; Pombeiro, A. J. L. Angew. Chem. Int. Ed., 2005, 44, 4345. 2.Kirillov, A. M.; Kopylovich, M. N.; Kirillova, M. V.; Karabach, E. Yu.; Haukka, M.; da Silva, M. F. C. G.; Pombeiro, A. J. L. Adv. Synth. Catal. 2005, 347, accepted. 3.Pombeiro, A. J. L.; Kirillov, A. M.; Kopylovich, M. N.; Kirillova, M. V.; Haukka, M.; da Silva, M. F. C. G. Patent pending PT 103225 (2005/01/19).


36

C-30- NEW WATER SOLUBLE ALLENYLIDENE RUTHENIUM COMPLEXES INCLUDING THE Cp(CONC(CH3)3)2 LIGAND

Antonio Romerosa, Mery Mallqui, Manuel Serrano-Ruiz

Área de Química Inorgánica. Universidad de Almería, 04120, Almería. Spain. E-mail:[email protected].

Water soluble metal complexes are an alternative to the most of catalytic processes used actually. This fact has leaded to an intense research activity centred on hydrosoluble metal complexes as an answer to the pressing request for developing more and more environmentally benign technologies in manufacturing of fine chemicals.1 We have recently started working in this hot area of chemistry and have demonstrated that ruthenium vinylidenes and allenylidenes stabilised by the water soluble phosphine m-TPPMS (TPPMS = m-mono-sulphonatedtriphenylphosphine) efficiently catalyzes the ROMP of cyclic alkenes2 and, the water soluble ruthenium complex [CpRuCl(PTA)2] (PTA = 1,3,5-triaza-7-phosphaadamantane) brings about the selective hydrogenation of benzylidene acetone in water.3,4 As a further step forward in this area, we report here the synthesis and the characterization of a family of water soluble metal complexes of formula [Ru{Cp(CONC(CH3)3)2}(X)LL’]n (Cpd =; X = halogen, allenylidene ligands; L= PPh3, PTA, mPTA, mTPPMS; L’ = PTA, mPTA, mTPPMS) (mPTA = methyl-1,3,5-triaza-7-phosphaadamantane). The aminoacid groups bonded to the Cp ring provide interesting electronic and steric properties to the complexes as well as better water solubility. These compounds show an interesting chemistry and particularly behave as efficient intermediates for stoichiometric and catalytical catalysts reactions in both water and biphasic aqueous conditions.

______________ References: 1. R. H. Grubbs, in Aqueous Organometallic Chemistry and Catalysis, I. T. Horváth, F. Joó, Eds.;

NATO ASI Ser. 3 5; Kluwer Academic Publishers, Dordrecht, The Netherlands, 1995, p. 15. 2. M: Saoud et al. Organometallics, 2000, 19, 4005-4007. 3. S. Bolaño et al J. Mol Cat. 2004, 224, 61-70. 4. D. Akbayeva et al, Chem. Comm. 2003, 264-265. ACKNOWLEDGEMENTS: AR thanks the

DGICYT (Spain) for PPQ2003-01339 and PAI (Junta de Andalucía, FQM-317). This work was supported by EC through the MCRTN program AQUACHEM (contract MRTN-CT-2003-503864) and the COST Actions D17 and D29.

Acknowledgements:



37

C-31- INTERMOLECULAR HYDROGEN BONDING BETWEEN NEUTRAL TRANSITION METAL HYDRIDES

(CpM(CO)3H, M = Mo, W) AND BASES

N. Belkova, O. Filippov, V. Levina, E. Gutsul, L. Epstein, E. Shubina

The interaction of CpM(CO)3H (M = Mo, W) hydrides as proton donors with different organic bases (pyridine, (n-Oc)3PO, (n-Bu)3PO) was studied by variable temperature IR spectroscopy and confirmed theoretically by DFT/B3LYP calculations. The data obtained show for the first time the formation of intermolecular hydrogen bonds between the neutral transition metal hydrides CpM(CO)3H and bases in solution; the result which does not have any precedent in the literature. These M-H…B hydrogen bonds are shown to precede the hydrides deprotonation.


38

C-32- NEW CLASSICAL AND NON-CLASSICAL HYDRIDES OF Ru(II) IN AQUEOUS SOLUTIONS

Gábor Papp

Institute of Physical Chemistry, University of Debrecen and Research Group of Homogeneous

Catalysis of the Hungarian Academy of Sciences, Debrecen 10, P.O.Box 7, H-4010 Hungary

We have described earlier that the selectivity of the hydrogenation of cinnamaldehyde catalyzed by the water soluble complex [{RuCl2(mtppms)2}2] (+ mtppms) was a sensitive function of the hydrogen pressure (mtppms = meta-monosulfonated triphenylphosphine). This effect was attributed to the shift of the equilibrium between the known [RuHCl(mtppms)3] and a dihydride, supposedly [RuH2(mtppms)4], although it was also noted that a new hydride species was formed at slightly elevated pressures of H2 (5-10 bar). The situation is even more complicated since the formation of the various hydride species is also strongly influenced by the pH of the aqueous solutions.

Recently we made detailed 1H and 31P NMR studies to establish the effects of the pH and the hydrogen pressure on the reaction of [{RuCl2(mtppms)2}2] (+ mtppms) and H2, including the determination of the relevant T1 and T2 relaxation times. The results revealed the formation of the following complexes:

a) in acidic solutions at 1 bar H2: [RuHCl(mtppms)3] and [{RuHCl(mtppms)2}2] b) in acidic solutions at elevated H2 pressures: trans-[RuH2(mtppms)4] c) in basic solutions at 1 bar H2: cis-[RuH2(H2O)(mtppms)3] d) in basic solutions at elevated H2 pressures: cis-[RuH2(H2)(mtppms)3].

Of these complexes, cis-[RuH2(H2)(mtppms)3] is a dihydrogen complex with water-soluble phosphine ligands and trans-[RuH2(mtppms)4] is one of the rare trans-dihydrides. (Furthermore, cis-[RuH2(H2O)(mtppms)3] was previously incorrectly described as cis-[RuH2(mtppms)4].)

POSTERS


40

P-1- NEW TRIS(PYRAZOLYL)METHANE VANADIUM

COMPLEXES: SYNTHESIS AND CATALYTIC ACTIVITY

Telma F.S. Silva1,2,3, Luísa M.D.R.S. Martins1,2 and Armando J.L. Pombeiro2

1Departamento de Engenharia Química, ISEL, R. Conselheiro Emídio Navarro, 1950-062

Lisboa, Portugal. 2 Centro de Química Estrutural, Complexo I, IST, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. 3 Área Científica de Física, ISEL, R. Conselheiro Emídio Navarro, 1950-062 Lisboa, Portugal.

E-mail:[email protected]

Although some vanadium compounds can display interesting catalytic properties, their application in catalysis is still an underdeveloped field of research. The conversion of alkanes into oxygenated derivatives (namely of cyclohexane into cyclohexanol and cyclohexanone, Scheme 1) has been extensively studied1 in view of the high industrial significance of such products.

V catalyst

H2O2, MeCNroom temp.

OH O

+

Scheme 1

Moreover, the chemistry of tris(pyrazolyl)methane transition metal complexes is currently attracting a high interest in particular due to the discovery of their application in catalysis and synthetic organometallic chemistry. Nevertheless, the coordination chemistry of tris(pyrazolyl)methanes at vanadium sites still remains very little explored.2

Herein we report the synthesis of new vanadium(IV) complexes with the N3 tripodal anionic tris(1-pyrazolyl)methanesulfonate SO3Cpz3

- (pz = pyrazolyl) ligand, which are water-soluble and can act as catalysts in the peroxidative oxidation of cyclohexane to cyclohexanone and cyclohexanol, by H2O2, under mild conditions in aqueous medium.

The new complexes have been characterized by IR and multinuclear NMR or EPR spectroscopies, FAB-MS spectrometry and elemental analysis. For the catalytic studies the turnover numbers and yields are indicated. ______________ References: 1. a) A. M. Kirillov, M. Haukka, M. Kirillova, A. J. L. Pombeiro, Adv. Synth. Catal. 2005, 347, 1435. b) A. M. Kirillov, M. N. Kopylovich, M. V. Kirillova, M. Haukka, M. F. C. G. da Silva, A. J. L. Pombeiro, Angew. Chem., Int. Ed. 2005, 44, 4345. c) A. M. Kirillov, M. Haukka, M. F. G. da Silva, A. J. L. Pombeiro, Eur. J. Inorg. Chem. 2005, 11, 2071. d) P. M. Reis, J. A. L. Silva, J. J. R. F. da Silva, A. J. L. Pombeiro, J. Mol. Cat. A. 2004, 224, 189. e) P. M. Reis, J. A. L. Silva, A. F. Palavra, J. J. R. F. da Silva, T. Kitamura, Y. Fujiwara, A. J. L. Pombeiro, Angew. Chem., Int. Ed. 2003, 42, 821. f) P. M. Reis, J. A. L. Silva, J. J. R. F. da Silva, A. J. L. Pombeiro, Chem. Commun. 2000, 1845. 2. Bigmore, R.H., Lawrence, S.C., Mountford, P., Tredget C.S., Dalton Trans. 2005, 635. Acknowledgements: This work has been partially supported by the AQUACHEM Project RTN nº MRTN-CT-2003-503864, the IPL/41/2003 project, the POCTI (FEDER funded) program and by the Fundação para a Ciência e Tecnologia (FCT), Portugal.


41

P-2- SELF-ASSEMBLY SYNTHESIS AND CHARACTERIZATION

OF NEW HETERODINUCLEAR AQUA COMPLEXES OF THE TYPE [M(H2O)5M′(dipic)2] (M, M′ = Co2+, Ni2+, Cu2+, Zn2+)

DERIVED FROM DIPICOLINIC ACID IN WATER SOLUTION

Marina V. Kirillova, M. Fatima C. G. da Silva, Alexander M. Kirillov, João J. R. Fraústo Da Silva, Armando J. L. Pombeiro

Centro de Quimica Estrutural, Complexo I, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-

001 Lisbon, Portugal; e-mail: [email protected], [email protected]

Dipicolinic acid (pyridine-2,6-dicarboxylic acid) is a water-soluble, cheap, commercially available and versatile N,O-chelator possessing diverse coordination modes, and with recognized biological function in a variety of processes namely in the body metabolism. Although a large quantity of dipicolinate complexes of almost all transition metals is known, no examples of heteronuclear 3d-metal complexes with this ligand have been reported up to date, while they can be of potential interest in biochemistry, catalysis, as magnetic materials, food supplements and water-soluble drugs.

Hence, we report here the synthesis and characterization of first heterodinuclear complexes of the type [M(H2O)5M′(dipic)2] (M, M′ = Co2+, Ni2+, Cu2+, Zn2+) with all possible combinations of these metals. Thus, the reaction of dipicolinic acid with binary M(II)/M′(II) nitrates in aqueous solutions at certain pH and at room temperature leads to the formation, by self-assembly and in high yield, of colored crystalline solids, which have been characterized by IR, UV/VIS and atomic absorption spectroscopies, elemental and X-ray diffraction single crystal analyses. All complexes are soluble and stable in water solutions from which they can be recrystallized. Atomic absorption spectroscopy confirms the presence, in equimolar amounts, of two different metals, while their assignment either to the cationic or the anionic part of the complexes is based on the characteristic absorption bands of the metal aqua species observed in UV/VIS spectra. The affinity of the metals to form anionic chelates with dipicolinate ligand is in the order Co > Ni > Zn > Cu, whereas the opposite dependance (Cu > Zn > Ni > Co) is observed for the formation of cationic aqua moieties. X-ray diffraction analyses indicate that the obtained complexes are isostructural and comprise two metal centres with distorted octahedral geometries, a typical representation of the crystal structure being shown in the Figure. All the dipicolinate oxygens, coordinated and crystallization water molecules are further involved into an O−H...O hydrogen bonding network, linking the molecular units and forming a three-dimensional infinite network.

This work has been partially supported by the Human Resources and Mobility Marie Curie Research Training Network (AQUACHEM project, CMTN-CT-2003-503864) and the Foundation for Science and Technology (FCT), and its POCTI programme (FEDER funded).


42

P-3- SYNTHETIC STRATEGIES FOR WATER SOLUBLE GOLD(I)

COMPLEXES

Elena Vergara, Elena Cerrada, Fabian Mohr, Mariano Laguna*.

Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón. Universidad de Zaragoza- C.S.I.C., 50009 Zaragoza, Spain.


Environmental as well as health and safety concerns relating to use of organic

solvents have increased the demand for “greener” alternatives. This has been the main driving force for the quest to obtain water soluble inorganic and organometallic complexes, one area of particular interest is the development of environmental benign chemistry using water as a reaction solvent.1 An important strategy for solubilising inorganic and organometallic compounds in water is by use of water soluble phosphine ligands as sulfonated arylphosphines, 1,3,5-triaza-7-phosphaadamantane (PTA) or 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA).2 Although PTA has been known since 1974,3 the coordination chemistry of this ligand, including some gold complexes, have only very recently been explored.4

Gold(I) thiolato and alkynyl complexes containing the phosphine ligands PTA

and DAPTA were prepared by reaction of the phosphinegold(I) chlorides with the thiol or alkyne in the presence of a base (Scheme 1). All the complexes were fully characterised by spectroscopic tecniques including NMR spectroscopy, mass spectrometry and infrared spectroscopy.

Very high water solubilities observed for the thiolatogold(I) complexes

including the 2-pyridine (51 g/L), 2-pyrimidine (50 g/L), 2- thiazoline (26 g/L), 4-methyl pyrimidine (125 g/L) derivates. Amongst the alkynylgold(I) complexes only the proparyl are soluble in water. However, solubility of these gold(I) complexes varies considerably: some compounds are completely insoluble in common organic solvents, some are poorly soluble in dmso or dmf, whilst others are soluble in halogenated solvents and acetone.


43

Scheme 1

[AuCl(P)] +

RSH

KOH[AuSR(P)]

HC CR´[Au (P)](C CR´)

KOH

P = DAPTA, PTA

RSH ≡

N SH

N SH

N

ESH

N

SSH

N

NSH

E= O, NH, S

R´CCH≡H

N H H H

H H H S H H

H

R2C

OH

R = H, Me, Ph R´≡ - tBu; -Ph; -Fc, OMe,

______________ References: 1. See for example (a) B. Cornils and W. A. Herrmann, in Aqueous-phase organmetallic catalysis concepts and applications, Wiley- VCH, Weinheim, 1998. (b) F. Joó, in Aqueous organometallic catalysis, Kluwer Academic Publishers, Dordrecht, 2001. 2. D. J. Darensbourg, C. G. Ortiz, and J. W. Kamplain, Organometallics, 23 (2004) 1747. 3. D. J. Daigle, A. B. Pepperman Jr., and S. L. Vail, J. Heterocyclic Chem., 11 (1974) 407. 4. See for example (a) A. D. Phillips, L. Gonsalvi, A. Romerosa, F. Vizza, and M. Peruzzini, Coord. Chem. Rev., 248 (2004) 955. (b) Z. Assefa, B. G. McBurnett, R. J. Staples, J. P. Fackler, Jr., B. Assmann, K. Angermaier, and H. Schmidbaur, Inorg. Chem., 34 (1995) 75. (c) C. Lidrissi, A. Romerosa, M. Saoud, M. Serrano-Ruiz, L. Gonsalvi and M. Peruzzini, Angew. Chem. Int. Ed., 44 (2005) 2568. (d) F. Mohr, E.Cerrada, M. Laguna, Organometallics in press.


44

P-4- WATER-SOLUBLE AND STABLE GOLD(II) COMPLEXES

Sergio Sanz, Fabian Mohr and Mariano Laguna

Departamento de Química Inorgánica, Instituto de Ciencias de Materiales de Aragón Universidad de Zaragoza-C.S.I.C, 50009 Zaragoza, Spain

Environmental concerns in the design of industrially important chemical processes has been the driving force in the exploration of water-based reactions. Using water soluble phosphine ligands, such as sulfonated arylphosphines 1,2,3 or 1,2,3-triaza-phosphaadamantane (PTA)4, it is possible to solubilise organometallic compounds. The gold(II) oxidation state is very rare in mononuclear compounds, but has been observed in metal-metal bonded digold complexes. In many cases, these digold(II) complexes are not stable, but either isomerise or undergo other reactions in solution. For these reasons, we were interested took up the challenge to prepare water-soluble and water stable digold(II) complexes. The digold(II) phosphine complexes were prepared by halide metathesis reaction from the dichlorodigold(II) compound and silver(I) salts of the phosphine (Scheme 1). All the complexes were characterised by NMR, mass spectrometry and, in the case of PTA, by X-ray crystallography.

Solubility in water ranges from 4g/L for the DAPTA and TPPMS complexes to 75g/L for the TPPTS complex. Aqueous solutions of the compounds remain unchanged for at least 7 days with no sign of decomposition.

Au Au

Ph2P

PPh2

ClCl2 [AgP]X

Au Au

Ph2P

PPh2

PP 2X-

2+

P =P

NNN

P

NNN

CH3H3COO

P P P

SO3Na SO3NaSO3Na SO3Na SO3Na

SO3NaPTA DAPTA TPPMS TPPDS TPPTS

______________ References: 1. F. Joó, J. Kovács, A. Kathó, A. Bényei, T. Decuir, and D. Darensbourg. Inorg. Synth., 1998, 32, 1. 2. T. Thorpe, S. Brown, J. Crosby, S. Fitzjohn, J. Muxworthy, and J. Williams. Tet. Lett., 2000, 41, 4503. 3. W. Herrmann, and C. Kohlpaintner. Inorg. Synth., 1998, 32, 8. 4. A.D. Phillips, L. Gonsalvi, A. Romerosa, F. Vizza, and M. Peruzzini. Coord. Chem. Rev., 2004, 955.


45

P-5- MAKING ORGANOMETALLIC SPECIES WATER-

SOLUBLE: PROPARGYL ALCOHOLS AS LIGANDS FOR GOLD(I) AND SILVER(I) COMPLEXES

Raquel Aroz, Fabian Mohr, Elena Cerrada and Mariano Laguna*

Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón

Universidad de Zaragoza- C.S.I.C., 50009 Zaragoza, Spain e-mail: [email protected]

Alkynyl complexes of gold(I) and silver(I) containing phosphine ligands have

been known for many years and have been studied in great detail due to their interesting luminescence, non-linear optical properties and supramolecular sturctures.1-3 The rapid development of “green chemistry” and the desire to be able carry out important industrial chemical processes in water has led to a surge in research in aqueous organometallic chemistry. For these reasons we were interested to attempt to prepare organometallic gold and silver complexes that are water-soluble and stable in water.

The strategy we employed to obtain water-soluble gold(I) and silver(I) alkynyl complexes was to utilize a combination of organometalic ligands with solubilising groups in combination with either the highly water soluble phosphine ligand TPA (1,3,5-triaza-7-phosphaadamantane) (Scheme 1)4 or soluble counter-ions such as nitrate (Scheme 2).5 The readily available propargyl alcohols, HC≡CCRRَOH ( R = Rَ = H, Me, and R = Me, Rَ = Et) seemed an obvious ligand choice due to the presence of a hydroxy group.

R = R` = H 1R = R` = Me 2R = R` = Ph 3R = Me, R` = Et 4

AuNN

NP Cl Au

NN

NP C OH

R`

RHC C C OH

R`

R

NaOEt

Scheme 1

3 AgNO3

HC CC

OH

R'

R

Et3N

3 dppm

Scheme 1

R = R' = H 1, Me 2R = Me, R' = Et 3

[Ag3(µ3-η1-C CCRR'OH)(µ-dppm)3](NO3)2

Scheme 2

The aim of producing water soluble organometallic gold(I) complexes was

indeed achieved: the TPA alkynyl gold(I) complexes 2 and 3 are soluble (ca. 8 g/l) and also stable in water. Surprisingly, complex 1 is only poorly soluble in water. However, the silver(I) clusters are not very soluble in water. Current work is in progress using bridging ligands that are more water-soluble than dppm. ______________ References: 1. Cheung, K. L.; Yip, S. K.; Yam, V. W. W., J. Organomet. Chem. 2004, 689, 4451. 2. Cifuentes, M. P.; Humphrey, M. A., J. Organomet. Chem. 2004, 689, 3968. 3. Mohr, F.; Jennings, M. C.; Puddephatt, R. J., Eur. J. Inorg. Chem. 2003, 217. 4. Mohr, F.; Cerrada, E.; Laguna, M., Organometallics in press. 5. Aroz, R.; Mohr, F.; Cerrada, E.; Laguna, M., J. Organomet. Chem. submitted.


46

P-6- RHODIUM COMPLEXES WITH PTA-BORANE ADDUCTS

Sandra Bolaño,a Alberto Albinati,a Luca Gonsalvi,b Louise Male,a Maurizio

Peruzzinib

a Dipartimento di Chimica Strutturale, Università di Milano, Via G. Venezian 21, 20133 Milano, Italy.

b Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organometallici (ICCOM-CNR), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy.


In recent years water-soluble phosphines have received an increasing interest due to their excellent ability to solubilize transition metal complexes in aqueous phase. Catalytic applications of metal complexes stabilised by this class of hydrosoluble ligands have been reported both in aqueous phase and biphasic homogeneous conditions. [1]

Among water soluble phosphines, particular interest has been paid to PTA (PTA = 1,3,5-triaza-7-phosphaadamantane) which is a versatile neutral cage-like ligand whose chemistry and catalytic activity has been recently reviewed. [2]

In this communication, we report on the synthesis and the characterization of two novel PTA-borane adducts, i.e. PTA(BH3) and PTA{B(OH)3}, and briefly describe their rhodium coordination chemistry. The reaction of [Cp*RhCl2]2 with either ligands produces the corresponding complexes [Cp*RhCl2{PTA(BH3)}] (1) and [Cp*RhCl2(PTA{B(OH3)})] (2) which were characterized by conventional spectroscopic methods and by X-ray single crystal diffraction analysis.

RhCl

ClP P

NN

NBH3Rh Rh

Cl

ClCl

Cl

+ 2 PTA(BH3)

THF

H2ORh

ClCl

NN

NB(OH)3

unsoluble in water water soluble

1 2

N N N N N N BH3N N N B(OH)3

BH3.THF H2O

+ PTA{B(OH)3}

P P P

___________ References: 1. Cornils, B; Herrmann, W.A. (Eds);, "Aqueous Phase Organometallic Catalysis” Wiley-VCH, Weinheim, 1997. b) Darensbourg, D. J; Decuir, T. J; Reibenspies, J. H; in: Horváth, I. T; Joó, F (Eds); "Aqueous Organometallic Chemistry and Catalysis", Kluwer, Dordrecht, 1995, pp. 61-80. 2. Phillips, A. D; Gonsalvi, L, Romerosa, A; Vizza, F; Peruzzini, M; Coord. Chem. Rev., 2004, 248, 955. Acknowledgements : Thanks are expressed to EC (RTN HYDROCHEM and AQUACHEM) and COST D29 to support this research activity.


47

P-7- CONVENIENT SYNTHESIS FOR [RuClCp(mPTA)2](CF3SO3)2

(mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane): INFLUENCE OF THE SOLVENT.

Pedro Gili-Trujillo,a Beatriz González,a Adrian Mena,a Pablo Lorenzo Luis,a

Tatiana Campos - Malpartida,b Manuel Serrano,b Chaker Lidrissi,b Vicente Jara-Pérez, b Antonio Romerosab

a Departamento de Química Inorgánica, Univesidad de La Laguna, 38204-La Laguna, Tenerife,

Canay Islands, Spain b Departamento de Química Física, Bioquímica y Química Inorgánica, Universidad de Almería,

04120, Almería, Spain. E-mail: [email protected]

The complex [RuClCp(mPTA)2](CF3SO3)2 (1) (mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane) was presented recently1 as an interesting water soluble ruthenium complex that is able to modified actively the DNA in very low concentrations (10.4 µM). The synthesis of this complex was accomplished by a complicate procedure that leaded to obtain the complex in very low yield. All tentative of obtain the complex in large yield by substitution of the PPh3 ligands in [RuClCp(PPh3)2] by mPTA by a similar procedure used for synthesizing similar complexes such as [RuClCp(PTA)2] (PTA = 1,3,5-triaza-7-phosphaadamantane)2 were not successful. The analysis preformed by DFT (Figure) leaded to the conclusion that the stability of the complex 1 is similar to that for [RuClCp(PPh3)(mPTA)](CF3SO3) (2) and suggesting that the experimental efforts must be focused to modified the reaction conditions. Finally 1 was obtained in high yield in similar reaction conditions to 2 but using a different reaction solvent volume.

______________ References: 1.Romerosa A.; Campos-Malpartida, T.; Lidrissi, C.; Saoud, M.; Serrano-Ruiz, M.; Peruzzini, M.; Garrido-Cárdenas, J. A.; García-Maroto. F. Inorg. Chem. 2005, IN PRESS 2.Akbayeva, D. N.; Gonsalvi, L.; Oberhauser, W.; Peruzzini, M.; Vizza, F.; Brüggeller, P.; Romerosa, A.; Sava, G; Bergamo, A. Chem. Comm. 2003, 264.


48

P-8- THEORETICAL STUDY OF POLAR DOUBLE BOND

HYDROGENATION BY MEANS OF THE SHVO CATALYST

Aleix Comas-Vives, Gregori Ujaque, Agustí Lledós

Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Catalonia E-mail: [email protected]

The {[2,3,4,5-Ph4(η5-C4CO)]2H}Ru2(CO)4(µ-H) complex (also known as “Shvo

catalyst”1) has been applied successfully in a broad range of hydrogen-transfer processes, such as: alkyne, carbonyl, and imine hydrogenations, alcohol and amine oxidations and also in kinetic dynamic resolution of secondary alcohols in combination with lipases.

It belongs to the so-called bifunctional catalysts, having two hydrogens of opposite acidic and hydridic properties, which are able to perform hydrogenation of polar double bonds with high efficiency.

Mainly, there are two mechanisms proposed in the literature for carbonyl hydrogenation. Whereas Casey proposed that the hydrogenation takes place via a concerted transition state outside the coordination sphere of the Ru atom,2 Bäckvall suggested that before hydrogen transfer, there is the C=O coordination via a η5 → η3 ring slippage of the Cp ring.3 Here, a theoretical study of the different proposed mechanisms is presented (see Figure 1). Other possibilities of carbonyl coordination like the CO leaving or the η5 → η2 Cp ring slippage have also been evaluated. In order to corroborate our results, kinetic isotope effects calculations have been made and compared with the reported experimental values.2

Figure 1. Energy profiles for the two proposed mechanisms.

_____________ References: 1. Shvo, Y.; Czarkie, D.; Rahamim, Y. J. Am. Chem. Soc. 1986, 108, 7400. 2. Casey, C. P. ; Singer, S. W. ; Powell, D. R. ; Hayashi, R. K. ; Kavana, M. J. Am. Chem. Soc. 2001, 123, 1090. 3. Csjernyik G.; Éll A. H.; Fadini, L.; Pugin, B.; Bäckvall, J.-E. J. Org. Chem. 2002, 67, 1657.


49

P-9- POLYSULFIDE SPECIATION IN AQUEOUS SYSTEMS

Ovadia Lev, Alexey Kamyshney, Jenny Gun

Casali Institute of Applied Chemistry, Department of Chemistry, The Hebrew University of

Jerusalem, Jerusalem 91904, Israel. E-mail: [email protected]

Inorganic polysulfides, Sn2- and their protonated forms contain sulfur in an

oxidation state between elemental sulfur and hydrogen sulfide. Polysulfides are always present in near - neutral and basic aqueous systems containing hydrogen sulfide and sulfur, and as such, they are important intermediates in the oxidation of hydrogen sulfide. Due to their redox reactivity and high nucleophilicity they are an important environmental family of precursors for transition metal ligation in aquatic systems as well as for cross linking of natural organic matter. Their role in the formation of volatile sulfur compounds including dimethyldisulfide, dimethyltrisulfide and carbonyl sulfide was recently explored by our laboratory. However, their reputation goes beyond the environmental arena. They are important for the paper and pulp industry, for photoelectrochemistry and energy storage as well as for metal finishing and decorative patina.

Although this set of compounds was investigated already by the founders of modern chemistry their speciation in aqueous systems continues to pose an analytical challenge until today. Recently we devised a new approach - based on rapid, single phase chemical methylation with methyl trifluoromethanesulfonate in order to determine the disproportionation constants and the underlying thermodynamics of inorganic polysulfides in aqueous solutions. This method resolved the dispute over the existence of hexasulfide in aqueous solutions and it establishes the presence of even higher polysulfide chains in water. The method was validated by isotope dilution and thorough kinetic studies and confirmed by ESI-MS investigation. A modified version of the approach was developed for determination of the individual members of the polysulfide family in natural aquatic systems. Iron and other transition metal ligation studies are underway.


50

P-10- SYNTHESIS OF SOME NEW BIOLOGICALLY ACTIVE COUMARIN

DERIVATIVES

N. Hamdia*, C. Lidrissib, L. Hajjia, M. Saoudb and Antonio Romerosab

a National Institute of Research and physico chemistry Analysis, technopole of sidi thabet 2020. Tunisia

Email: [email protected] b Dpto.Quimica Fisica, Bioquimica y Quimica Inorganica, Universidad de Almeria, Almeria,

Spain. E-mail: [email protected]

The reaction of 4-hydroxycoumarin in toluene with a varieties of aromatic binucleophilic compounds has been studied to form selectively (2-hydroxyphenyl)-2,3-dihydro-1H-1,5-benzodiazepin-2-one compound 3 (Scheme 1-a).

In addition, 3-(dimethylaminomethylene)chromane-2,4-dione was used as a key intermediate for the preparation of bis N-(methylene-4-oxocoumarinyl)-1,4- diamines (Scheme 1-b). An interesting result was achieved, no inter and/or intramolecular nucleophilic attack took place on the two carbonyl function.

Alternative synthetic procedures and the biological activities of some new compounds are given. The structures of the obtained products have been assigned by means of spectroscopic measurements.

O

NNHOH

NH2

NH2+

O O

OH

O

NNHOH

H

i iiOH

HN

N

OHO

HN

NOH

OH

HN

N

B

A A'3

i. Toluene,

4

O

N(Me)2

O

O+

NH2

H2N

O

O

O N

NH

OO

OH

toluenereflux

6

7a

4h

b

a

ii. Conc. H2SO4 ,

Scheme 1

______________ References: 1. Kelkar, R. M.; Joshi, U. K.; Paradkar, M. V. Synthesis, 1986, 214. 2. Moppet, R. B. J. Med. Chem. 1964, 7, 446. 3. G. Redighiero, C. Antonello, Bull. Chim. Farm. 1985, 97, 592.

Acknowledgements

Authors thank PAI (Junta de Andalucía, FQM-317) and “Consejería de la Presidencia” (Junta de Andalucía) For the projects AM56/04 and AM55/04.


51

P-11- NEW WATER SOLUBLE Ru COMPLEXES AND THEIR

PHOTOCHEMICAL ACTIVITY

Laura Martos, Sonia Mañas, Antonio Romerosa

Área de Química Inorgánica. Universidad de Almería, 04120, Almería. Spain. E-mail: [email protected]; [email protected]

It is well known the great importance of Ru complexes as catalysts in a lot of inorganic and organic reactions. Lately the studies of organometallic Ru compounds have been focused in order to obtain water soluble complexes due to numerous advantages: economical, non toxic for the environment (“Green Chemistry”), etc. However there are no many complexes which present this fundamental characteristic.

For this reason our team in Almería is studying Ru compounds containing water soluble ligands as PTA (1,3,5-triaza-7-phosphaadamantane), mTPPMS (m-sulphonated triphenylphosphine, mPTA (methyl-1,3,5-triaza-7-phosphaadamantane); the use of these ligands increase the organometallic compounds solubility polar solvents.

Recently we have synthesised an interesting new water soluble Ru compound octahedrically coordinated to four mPTA and two Cl ligands. (scheme 1) This new compound is very soluble in water and presents reactivity towards several nucleophiles such as amines, thiols, etc., giving rise different compounds depending on whether or not the reaction is irradiated by solar light.

RuCl2(PPh3)3CH3

NN

N

PEtOH

CF3SO3∆

RuCl

Cl

CH3N

NN

PH3C

NN

N

P

H3C NNN

P

CH3

N N

NP

[CF3SO3]4

Scheme 1

+ 3

Acknowledgements: Thanks are given to PAI (Junta de Andalucía, FQM-317), MCYT (Spain) for the project PPQ2003-01339, the MCRTN program AQUACHEM (MRTN-CT-2003-503864) and the COST Actions D17 and D29.


52

P-12- PURINE INTERACTION TOWARD [RuClCp(PPh3)(PTA)]

Gaspar Segovia Torrente, Cristóbal Saraiba Bello, Manuel Serrano Ruiz,

Antonio Romerosa

Departamento de Química Física, Bioquímica y Química Inorgánica, Universidad de Almería, 04120, Almería, Spain.


The interesting binding properties of the new hydrosoluble ruthenium(II) chiral complexes [RuCpX(L)(L’)]n+ (X = Cl, I. L= PPh3; L’ = PTA, mPTA; L = L’ = PTA, mPTA) (PTA = 1,3,5-triaza-7-phosphaadamantane; mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane) towards DNA have been studied using the mobility shift assay. It is very important to determine the coordination mode of the new water soluble complexes to DNA in order to obtain more DNA active complexes.1 By reaction in ethanol of [RuClCp(PPh3)(PTA)] with KOH and thio-purine 8-methyl-thioteophylline (8MTTH) a complex containing a deprotonated purine molecule bonded to the metal by the S atom was obtained, instead of the expected N7 purine coordination (Figure).

N

O

F

P

S

Ru

References: 1. Romerosa A.; Campos-Malpartida, T.; Lidrissi, C.; Saoud, M.; Serrano-Ruiz, M.; Peruzzini, M.; Garrido-Cárdenas, J. A.; García-Maroto. F. Inorg. Chem. 2005, IN PRESS Acknowledgements: Thanks are given to PAI (Junta de Andalucía, FQM-317), MCYT (Spain) for the project PPQ2003-01339, the MCRTN program AQUACHEM (MRTN-CT-2003-503864) and the COST Actions D17 and D29.


53

P-13- EPOXIDATION OF ALKENES IN IONIC LIQUID USING CHEAP MOLYBDENUM (VI) COMPOUNDS AS CATALYSTS

Matthew Herbert, Francisco Montilla, Antonio Pastor, Agustín Galidno

Dpto. Química Inorgánica. Fac. Química. Universidad de Sevilla. 41071 Sevilla, Spain.

E-mail: [email protected] Epoxidation of alkenes is an important synthetic transformation, allowing the conversion of simple substrates into valuable precursor in the synthesis of fine chemicals. Catalysis of these reactions by transition metal complexes is therefore an important area of research. Oxygen aside, hydrogen peroxide is the most economical and environmentally benign of the potential oxidants to be used in epoxidations.1 Organomolybdenum oxides make less effective catalysts in olefin epoxidations than organorhenium oxides2 and normally employ organic peroxides, such as tert-butyl hydroperoxide, as oxidant.3 Only recently has an efficient molybdenum catalyzed epoxidation using hydrogen peroxide as oxidant been described.4 Over the past decade room temperature ionic liquids (RTIL’s) have received interest as potential alternatives to commonly used organic solvents due to their unique physical properties. RTIL’s can solubilise many inorganic compounds, whilst being immiscible with several common extraction solvents meaning that a catalyst can often be immobilised in the ionic liquid whilst products are separated by extraction, allowing the catalyst to be recycled.5 The use of RTIL’s in molybdenum catalysed olefin epoxidation has been previously reported.4,6 In this communication we present our preliminary results in the epoxidation of olefins using [bmim][PF6] ionic liquid as reaction solvent, urea hydrogen peroxide (UHP) as oxidant and several common molybdenum (VI) compound as catalysts. The catalyst-ionic liquid solution proved to be removable and, after extraction of the epoxide product, was reused with further catalytic cycles showing no loss of efficiency.

"Mo(VI)"/UHP

[bmim][PF6]

NN

PF6-

[bmim][PF6]:

O

References: 1. (a) Fioroni, G.; Fringuelli, F.; Pizzo, F.; Vaccaro, L. Green Chem., 2003, 5,1. (b) Lane, B. S.; Burguess, K. Chem. Rev., 2003, 103, 2457. 2. Kühn, F. E.; Santos, A. M.; Herrmann, W. A. Dalton Trans., 2005, 2483. 3. See for example: Kühn, F. E.; Zhao, J.; Abrantes, M.; Sun, W.; Afonso, C. A. M.; Branco, L. C.; Gonçalvez, I. S.; Pillinger, M.; Romão, C. C. Tetrahedron Lett., 2005, 46, 47 and references therein. 4. Gharah, N.; Chakraborty, S.; Mukherjee, A. K.; Bhattacharyya, R. Chem. Commun., 2004, 2630. 5. A general reference is: Wasserscheid, P.; Welton, T. Ionic Liquids in Synthesis, Wiley-VCH, 2003. 6.Valente, A. A.; Petrovski, Ž.; Branco, L. C.; Afonso, C. A. M.; Pillinger, M.; Lopes, A. D.; Romão, C. C.; Nunes, C. D.; Gonçalvez, I. S. J. Mol. Catal. A: Chem. 2004, 218, 5.


54

P-14- DNA BINDING OF NEW WATER SOLUBLE

CYCLOPENTADIENYL RUTHENIUM(II) COMPLEXES INCORPORATING PHOSPHINES

Jose Antonio Garrido-Cárdenas, Federico García-Maroto, Antonio Romerosa,

Tatiana Campos-Malpartida, Chaker Lidrissi, Mustapha Saoud, Manuel Serrano-Ruiz.

Departamento de Química Física, Bioquímica y Química Inorgánica, Universidad de Almería,

04120, Almería, Spain

The binding properties towards DNA of the new hydrosoluble ruthenium(II) chiral complexes [RuCpX(L)(L’)]n+ (X = Cl, I. L= PPh3; L’ = PTA, mPTA; L = L’ = PTA, mPTA) (PTA = 1,3,5-triaza-7-phosphaadamantane; mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane) have been studied using the mobility shift assay on plasmid DNA. The ruthenium chloride complexes interact with DNA depending on the hydrosoluble phosphine bonded to the metal, while the corresponding compounds with iodide, [RuCpI(PTA)2] (1), [RuCpI(PPh3)(PTA)] (3), [RuCpI(mPTA)2](OSO2CF3)2 (6) and [RuCpI(mPTA)(PPh3)](OSO2CF3) (9), do not bind to DNA (Figure 1).

Figure 1. DNA mobility shift assay for the water soluble ruthenium complexes. Plasmid DNA was incubated with [RuClCp(PTA)2] (panel A), [RuCpI(PTA)2] (1) (panel B), [RuClCp(PPh3)(PTA)] (2) (panel C), [RuCpI(PPh3)(PTA)] (3) (panel D), [RuClCp(mPTA)2](OSO2CF3)2 (5) (panel E), [RuCpI(mPTA)2](OSO2CF3)2 (6) (panel F), [RuClCp(mPTA)(PPh3)](OSO2CF3) (7) (panel G) and [RuCpI(mPTA)(PPh3)](OSO2CF3)2 (9) (panel H). Ri values (Ru/base molar ratio) in the different assays were: 0, 5.3, 8.0, 10.7, 13.3, 16.0, 21.3, 26.7 (lanes 1 to 8 of panel A); 0, 5.3, 8.0, 10.7, 13.3, 16.0, 21.3, 26.7, 32.0 (1-9 panel B); 0, 2, 4, 5, 6, 7, 8, 10, 11 (1-9 panel C); 0, 2, 4, 6, 8, 10, 12, 15 (1-9 panels D and F); 0, 0.4, 0.8, 1.2, 1.6, 2, 2.4, 3 (1-8 panel E); 0, 0.33, 0.66, 1.0, 1.3, 1.7, 2.0, 2.5 (1-8 panels G and H).


55

P-15- SYNTHESIS IN WATER OF THE NEW SILVER PYRIMIDINE

POLYMER [AgC4N3H6NO3]n

Vicente Fernández,a Antonio Romerosa.b

a Departamento de Química Inorgánica.Universidad Autónoma de Madrid.28049 Madrid(Cantoblanco), Spain. [email protected].

bÁrea de Química Inorgánica. Universidad de Almería, 04120, Almería. Spain. [email protected].

Silver complexes are among the most interesting compounds. The ability of the silver metal to adopt different coordination geometry depending on ligands and reaction conditions have leaded to obtain a plethora of silver complexes characterized by interesting optical, electrical, electronic properties.1,2,3 Instead of the interesting silver complexes obtained with differentiate features few is made about aqua-soluble silver complexes and the study of their properties in water solution. By reaction of silver nitrate with 2-amino-pyrimidine in aqueous solution a new 3D extended silver polymer was obtained. Its crystal structure is made of tetra-silver rings in which the metal atoms are bonded alternatively by NO3

- and C4N3H5 ligands.

References: 1. Chun-Long Chen, Chen-Yong Su, Yue-Peng Cai, Hua-Xin Zhang, An-Wu Xu, Bei-Sheng Kang, Hans-

Conrad zur Loye, Inorg. Chem. 2003,42,3738. 2. Carolyn J. Shorrock, Bao-Yu Xue, Peter B. Kim, Raymond J. Bachelor, Brian O. Patrick, Daniel B.

Leznoff. Inorg. Chem. 2002,41,6743. 3. Yu-Bin Dong, Jun-Yan Cheng, Ru-Qi Huang, Mark D. Smith, Hans-Conrad zur Loye. Inorg. Chem.

2003,42,5699.


56

P-16- A NEW CLASS OF VINYLIDENE RUTHENIUM(II) WATER

SOLUBLE COMPLEX WITH ACID CHARACTER

M. Saoud, Antonio Romerosa

University of Almería, Dpt. of Inorganic Chemistry, Spain Email: [email protected]

The synthesis of the first transition-metal vinylidene complex and the discovery

of the first transition-metal carbene complexes by Ficher and Maasbol in 19641 constitute the starting point of a fecund research line in chemistry. These species are characterized by a rich activity including to mediate C-C and C-heteroatom coupling reactions2 and its contribution in many catalytic processes as the intermediary necessary in the metathesis reactions.3 Carbene metal complexes are synthesized by protonation of the metal vinyllidene or alkynylidene complex which are formed by metal activation of terminal acethylenes.4 In this communication we present a new water soluble vinylidene complex characterized to be a hard acid in water. This complex does not react with alcohols neither with acids, reacting slowly with nucleophilic molecules such as thiols and water in which is stable for 1 day.

RuCl

PP

Ru CP

P C H

Ph

RuC

PP

CPh

Amines

H+

no reaction

H+

HCCPh

+

P = PPh2(PhSO3Na)

H2Oslowly

HSEtslowly

RuCO

PP

+

Ru CP

P

CH2Ph

SCH2CH3

+

1

2 34

5 Scheme

References: 1. Fischer, E. O.; A. Angew . Chem., Int. Ed. Engl. 1964, 3, 580 2. V. Cadierno, J. Díez, J. García-Álvarez, and J. Gimeno, Organometallics 2005, 24, 2801-2810. 3. a) H. Katayama, H. Urushima, F. Ozawa, J. Organometallic. Chem., 2000, 606, 16. b) M. Saoud, A. Romerosa, M. Peruzzini, Organometallics, 2000, 19, 4005. c) H. Hamidov, J. C. Jeffery and Ja. M. Lynam, Chem. Commun., 2004, 1364-1365. 4. M. I. Bruce and R. C. Wallis, Aus. J. Chem., 1979, 32, 1471. Acknowledgements: Thanks are given to PAI (Junta de Andalucía, FQM-317), MCYT (Spain) for the project PPQ2003-01339, the MCRTN program AQUACHEM (MRTN-CT-2003-503864) and the COST Actions D17 and D29.


57

P-17- CRYSTAL STRUCTURE OF A NEW Cp Ru COMPLEX

SUBSTITUTED BY THREE DIFFERENT PHOSPHINE

Chaker Lidrissi, Antonio Romerosa, Manuel Serrano, Sonia Mañas

Área de Química Inorgánica. Universidad de Almería, 04120, Almería. Spain. [email protected]; [email protected]

Several studies have shown that Ru(II) complexes are very important in biological and catalytical processes.1 The interest in this field is increasing due to the necessity of obtaining new compounds environmental ecobenign and easily to synthesise.

In our research group it has been synthesised a new family of Cp Ru complex containing different combinations of phosphine such as PTA (1,3,5-triaza-7-phosphaadamantane), mPTA (methyl-1,3,5-triaza-7-phosphaadamantane) and PPh3 (tristriphenylphosphine). Here we report the crystal structure of a Ru (II) compound substituted by three different ligands, [RuCp(PPh3)(PTA)(m-PTA)](CF3SO3)Cl. (Figure).

Figure 1. Crystal structure of [RuCp(PPh3)(PTA)(m-PTA)](CF3SO3)Cl

____________ References: 1. Antonio Romerosa, Tatiana Campos-Malpartida, Chaker Lidrissi, Mustapha Saoud, Manuel Serrano-Ruiz, Mauricio Peruzzini, José Antonio Garrido-Cárdenas, Federico García-Maroto, Inorganic Chemistry, in press.

PARTICIPANTS LIST


59

PARTICIPANTS LIST

Aroz Palacios, Raquel Instituto de Ciencias de los Materiales de Aragón - Spain [email protected] Bastos Alegría, Elisabete Instituto Técnico Superior Lisboa – Portugal [email protected] Belkova, Natalia A.N. Nesmeyanov Institute of Organoelement Comp – Russia [email protected] Bolaño García, Sandra University of Vigo – Spain [email protected] Bravo Bernárdez, Jorge University of Vigo – Spain [email protected] Boulaid, Mourad University of Almería – Spain [email protected] Brausam, Ariane University Erlangen-Nürnberg, Instit for In.Chem – Germany [email protected] Caminade, Anne-Marie CNRS – France [email protected] Campos Malpartida, Tatiana University of Almería – Spain [email protected] Ciardi, Chiara University of Almería - Spain [email protected] Comas-Vives, Aleix Universitat Autonoma Barcelona – Spain [email protected] Dinoi, Chiara LCC (CNRS) – France [email protected]


60

Fernández Barbero, Antonio University of Almería – Spain [email protected] Fouad Bachir, Abdel Ouahab University of Malek Es-saâdi – Moroco García, Federico University of Almería – Spain [email protected] Garrido Cárdenas , Jose Antonio University of Almería – Spain [email protected] Garzón, Eduardo University of Almería – Spain [email protected] Gili, Pedro Universidad de la Laguna – Spain [email protected] Gimeno, José University of Oviedo – Spain [email protected] Gonsalvi, Luca ICCOM-CNR – Italy [email protected] González del Castillo, Beatriz University of La Laguna – Spain [email protected] González Mosquera, Marta Elena University of Alcalá – Spain [email protected] Gun, Jenny The Hebrew University of Jerusalem – Israel [email protected] Gutkin, Vitaly The Hebrew University of Jerusalem – Israel [email protected] Hajii,Lazhar University of Almería – Spain [email protected]


61

Hamdi, Naceur National Institute of Research and physic. Analysis – Tunisia [email protected] Hayes, Joe University Autonomous Barcelona – Spain [email protected] Herbert, Mathew University of Sevilla – Spain [email protected] Jara-Pérez, Vicente University of Almería – Spain [email protected] Jesús Alcáñiz, Ernesto de University of Alcalá – Spain [email protected] Joo-Eun Jee University Erlangen-Nürnberg, Instit for In.Chem – Germany [email protected] Joo, Ferenc University of Debrencen – Hungary [email protected] Katho, Agnes University of Debrencen – Hungary [email protected] Karabach, Yauen Insituto Superior Tecnico – Portugal [email protected] Kirillov, Alexander Instituto Superior Tecnico I.S.T – Portugal [email protected] Kirillova, Marina Insituto Superior Técnico – Portugal [email protected] M. Cruz, Adrián University of La Laguna – Spain [email protected]


62

Labande, Agnes Laboratoire de Chimie de Coordination-CNRS – France [email protected] Lev, Ovadia The Hebrew University of Jerusalem – Israel [email protected] Lidrissi, Chaker University of Almería – Spain [email protected] Lledós, Agustí Universitat Autònoma de Barcelona – Spain [email protected] Lorenzo-Luis, Pablo Antonio University of La Laguna – Spain [email protected] Mallqui, Inocenta Mery University of Almería – Spain [email protected] Manoury, Eric Laboratoire de Chimie de Coordination-CNRS – France [email protected] Mañas Carpio, Sonia University of Almería – Spain [email protected] Martins, Luisa Instituto Superior Técnico – Portugal [email protected] Martos, Laura University of Almería – Spain [email protected] Mena, Adrían University of La Laguna-Spain [email protected] Montilla, Francisco University of Sevilla – Spain [email protected]


63

Moreno, Abel Institute of Chemistry – Mexico [email protected] Papp, Gabor University of Debrencen – Hungary [email protected] Perutz, Robin University of York – England [email protected] Peruzzini, Maurizio ICCOM CNR – Italy [email protected] Petersen, Emma University of Almería – Spain [email protected] Poli, Rinaldo CRNS-LCC – France [email protected] Pombeiro, Armando Instituto Superior Tecnico – Portugal [email protected] Prikhodchenko, Petr The Hebrew University of Jerusalem – Israel [email protected] Reddig, Nicole University of York – England [email protected] Romerosa Nievas, Antonio Manuel University of Almería – Spain [email protected] Sainz Herrán, Nuria University of Almería – Spain [email protected] Sánchez Bajo, Lourdes Fundación CTAP – Spain [email protected]


64

Sanz Calvo, Sergio Instituto de Ciencias de los Materiales de Aragón – Spain [email protected] Saraiba Bello, Cristóbal University of Almería – Spain [email protected] Saoud, Mustapha University of Almería – Spain [email protected] Serrano Ruiz, Manuel University of Almería – Spain [email protected] Servin, Paul LCC/CNRS – France [email protected] Segovia Torrente, Gaspar Francisco University of Almería – Spain [email protected] Silva, Telma Instituto Técnico Superior – Portugal [email protected] Vergara Torralba, Elena Instituto de Ciencias Materiales de Aragón (ICMA) – Spain [email protected] Wojtkow, Wojciech University of Debrencen – Hungary [email protected] Zeric, Snezana University of Belgrade - Serbia and Monenegro [email protected]


65

AUTHOR’S INDEX

A

Albinati Alberto P-6

Alegria Elisabete C-10, C-11 Aroz Raquel P-5

B Baya Miguel C-2, C-23 Belkova N. C-19, C-31

Bolaño Sandra P-6

Brausam Ariane C-16

Bruneau Christian PL-2

C

Cagatay Bahar C-2

Caminade Anne-Marie C-12, c-22

Campian Marius V. C-17

Campos-Malpartida Tatiana C-1, P-7, P-14

Cerrada Elena P-3, P-5

Ciardi Chiara C-7

Comas-Vives Aleix P-8

D

Da Silva M. Fatima C.G. C-3, C-29, P-2

Daran Jean-Claude C-2, C-20, C-23 Demir Deniz C-2

Demirhan Funda C-2, C-23


66

Dinoi Chiara C-23

Duckett Simon B. C-27

Duhme-Klair Anne-K. C-27 E Epstein L. C-31

F

Fernández Amadeo C-21

Fernández Barbero Antonio C-4

Fernández Vicente P-15

Filippov O. C-31

Fraústo Da Silva Joao J.R. P-2

G

Galindo Agustín C-15, P-14

García-Maroto Federico P-14

Garrido-Cárdenas Jose Antonio P-14

Gili-Trujillo Pedro P-7

Gimeno José PL-1

Gonsalvi Luca C-7, C-9, P-6

González Beatriz P-7

Gun Jenny C-5, C-25, P-9

Gutkin Vitaly C-25 Gutsul E. C-31 H Hajji.L P-10


67

Hamdi N. P-10

Haukka Matti C-3, C-29

Herbert Matthew C-15, P-13

J

Jara-Pérez Vicente P-7 Jee Joo-Eun C-28 Joó Ferenc C-6, C-26

Juranic Nenad O. C-13

K

Kamyshney Alexey P-9

Karabach Yauhen Yu. C-3, C-29

Kirillov Alexander M. C-3, C-29, P-2

Kirillova Marina V. C-3, P-2

Kopylovich Maximilian N. C-3, C-29

Kovács Gabor C-26

L

Labande Agnés C-20

Laguna Mariano P-3, P4, P-5

Landaeta Vanessa C-9

Laurent Régis C-12, C-22

Lev Ovadia C-5, C-25, P-9 Levina V. C-31

Lidrissi Chakeer P-7, P-10, P-14, P-17

Lindup Richard J. C-17


68

Lledós Agustí C-14, C-26, P-8

Lorenzo Luis Pablo P-7

M

Majoral Jean-Pierre C-12, C-22

Malacea Raluca C-20 Male Louise P-6

Mallqui Mery C-30

Manoury Eric C-20

Mañas Carpio Sonia P-11, P-17

Marder Todd B. C-17

Martins Luísa C-10, C-11, P-1

Martos Artero Laura P-11

Medakovic Vesna B. C-13

Melman Artem C-5 Mena Adrián P-7

Milcic Milos K. C-13 Mohr Fabian P-3, P-4

Montilla Francisco C-15, P-13 Moreno Abel C-8

P

Paap Gabor C-32

Pastor Antonio C-15, P-13

Perutz Robin N. C-17, C-27

Peruzzini Maurizio C-7, C-9, P-6

Poli Rinaldo C-2, C-20, C-23

Pombeiro Armando C-3, C-10, C-11, C-18, C-30, P-1, P-2


69

Prikhodchenko Petr V. C-25

R

Redding Nicole C-27

Reginato Gianna C-7

Romerosa Antonio C-1,C-7, C-31, P-7, P-10, P-11, P-14, P-15, P-16, P-17

Rossin Andrea C-26

Routaboul Lucie C-20 S Sanz Sergio P-4

Saoud Mustapha P-10, P-14, P-16

Saraiba Bello Cristobal P-12

Segovia Torrente Gaspar P-12

Serrano-Ruiz Manuel C-7, C-30, P-7, P-12, P-14, P-17 Servin Paul C-12, C-22 Shubina E. C-19, C-31 Silva Telma C-10, P-1

Sredojevic Dusan N. C-13

T

Taban Gülnur C-23

Theodoridis Alexander C-16, C-29

U

Ujaque Gregori C-26, P-8


70

V

Van den Berg Constant M.G. C-5

Van Eldik Rudi C-16, C-28, C-29

Vergara Elena P-3

W

Wojtkow Wojciechw C-24

Wolak Maria C-16, C-28, C-29 Wolf Joffrey C-20 Z Zahl Achim C-28

Zaric Snezana D. C-13

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