highly hindered monophosphines for isolation and ... · pdf filescheme 1 - ethylene ... g gram...
TRANSCRIPT
Highly hindered monophosphines for isolation and reactivity of low
valent nickel complexes
Tiago Joo Neves
Thesis to obtain the Master of Science Degree in
Chemical Engineering
Supervisors: Pierre-Alain Breuil
Typhene Michel
Prof. Ana Margarida Martins
Examination Committee
Chairperson: Prof. Jos Manuel Madeira Lopes
Supervisor: Prof. Ana Margarida Martins
Members of the Committee: Prof. Pedro Teixeira Gomes
28th October 2016
[This page is intentionally left blank]
A book is proof that humans are capable of working magic
Carl Sagan
[This page is intentionally left blank]
Remerciements
Je dois, tout d'abord, remercier IFP nergies Nouvelles et Madame Hlne Olivier-Bourbigou
de m'avoir accueilli au sein du dpartement de Catalyse Molculaire, pour la dure de mon stage.
Je souhaite aussi remercier Pierre-Alain Breuil et Typhne Michel, responsables de mon
stage, tant pour leur disponibilit que pour leurs conseils scientifiques et techniques aviss. galement,
je souhaite exprimer ma gratitude Emile Moser, doctorant tudiant dans lequel mon stage tombe,
pour tout le soutien, le temps, l'enseignement et la patience quil ma consacr pendant mon sjour
l'IFP nergies Nouvelles.
Je remercier, en outre, trs chaleureusement Emmanuel Pellier, mon technicien rfrent, pour
mavoir form aux pratiques de laboratoire, partager avec moi ses connaissances et ses bonnes
blagues. J'adresse aussi mes remerciements Olivia Chaumet-Martin, Sverine Forget, Sandrine
Berard et Sbastien Drochon pour avoir pris le temps de me former aux diffrentes techniques
ncessaires la ralisation de ce projet.
Je remercie les membres, permanents ou non, de lquipe du dpartement Catalyse
Molculaire avec qui j'ai eu le plaisir de travailler.
Finalement, je remercie tous les stagiaires du bureau 2F1B et toutes les personnes qui m'ont
aid apprendre le franais.
[This page is intentionally left blank]
Resumo
O objetivo deste projeto consistiu na conceo de novas estruturas e catalisadores para
oligomerizao seletiva do etileno.
Para atingir este objetivo, e baseando-nos na literatura disponvel, foram selecionadas
potenciais monofosfinas ligantes com base nas suas propriedades eletronegativas e de impedimento
estereoqumico.
O ligantes desejados foram sintetizados com sucesso, e quando possvel adquiridos
comercialmente.
Palavras-chave: Nquel, monofosfinas, oligomerizao, etileno.
[This page is intentionally left blank]
Abstract
This work fall within the context of the conception of new structures and catalysts for ethylene
oligomerization.
Based on literature, potential monophoshines ligands were selected, based on their
electronegative properties and hindrance.
The desired ligands were synthesised, with success, when they were not commercially
available.
Keywords: Nickel, monophosphines, oligomerisation, ethylene.
[This page is intentionally left blank]
Table of Contents Remerciements ........................................................................................................................................ v
Resumo ................................................................................................................................................... vii
Abstract ................................................................................................................................................... ix
List of Figures .......................................................................................................................................... xii
List of Tables ........................................................................................................................................... xii
List of Schemes ....................................................................................................................................... xii
Abbreviations ......................................................................................................................................... xv
1 Introduction and Scope ........................................................................................................................ 1
1.1 Context .................................................................................................................................... 1
1.2 State of Art .............................................................................................................................. 4
1.2.1 Cossee-Arlman Mechanism vs Metallacycle Mechanism ................................................ 4
1.2.2 Catalysts based on Nickel ................................................................................................ 6
1.3 Aim of the project.......................................................................................................................... 9
2 Results and Discussion........................................................................................................................ 11
2.1 Monophosphine ligands .............................................................................................................. 11
2.1.1 Buchwald Phosphines ........................................................................................................... 11
2.1.2 Anionic phosphines .............................................................................................................. 15
2.2 Silicon and Tin moieties ............................................................................................................... 18
3 Experimental Part ............................................................................................................................... 20
3.1 General procedures ..................................................................................................................... 20
3.2 Ligands Synthesis ......................................................................................................................... 21
4 Conclusion .......................................................................................................................................... 25
5 Bibliography ........................................................................................................................................ 27
Appendix I - Tolmans map .................................................................................................................... 29
Appendix II Ligands Spectra ................................................................................................................ 30
List of Figures Figure 1- The two main families of Ni active catalysts [1]. ..................................................................... 6
Figure 2 - General form of a typical SHOP catalysts by Keim et al. ......................................................... 8
Figure 3 - Some examples of ligands that can coordinate Nickel............................................................ 8
Figure 4 - Selected Buchwald phosphines: L1 and L2 synthetized; L3 and L4 commercially available. 11
Figure 5 - White crystals of L1. .............................................................................................................. 12
Figure 6 - Second group of selected monophosphines. ........................................................................ 14
Figure 7 - (2-phenylindenyl)dicyclohexylphosphine (neutral L8; anionic L9) [18]. ............................... 15
Figure 10 - White powder of tpvt after dried. ....................................................................................... 19
List of Tables Table 1 - Market survey of alpha olefins production [2]. ........................................................................ 1
Table 2 - Importance of LAO for the plastics industry (LLDPE and HDPE) [3]. ........................................ 1
Table 3 - Different use of alpha olefins in industry depending on their chain length [3]. ...................... 1
Table 4 - On purpose processes for selective production of 1-butene, 1-hexene and 1-octene [1]. ...... 2
Table 7 - Structure and purity of the synthetized ligands. .................................................................... 25
Table 8 - Structure of the commercial ligands. .................................................................................... 25
List of Schemes Scheme 1 - Ethylene oligomerization mechanisms: degenerative polymerization (route A),
metallacycle pathway (route B) [1]. ........................................................................................................ 4
Scheme 2 - Activation mechanism with dichloroethylaluminum. .......................................................... 7
Scheme 3 - Example of SHOP catalyst formation by Keim. ..................................................................... 7
Scheme 4 - Synthetic route to (2-cyclohexylphenyl)biphenyl-phosphine (L1). ...................................... 12
Scheme 5 -Synthetic route to (2-diphenyl)biphenyl-phosphine (L2). .................................................... 13
Scheme 6 - Synthetic route to Di-tert-butylisopropylphosphine (L6). ..................................................