Issue 35, 2011
From the journal:

Dalton Transactions

Mono N,C,N-pincer complexes of titanium, vanadium and niobium. Synthesis, structure and catalytic activity in olefin polymerisation†

Alexey V. Chuchuryukin,ae   Rubin Huang,de   Ernst E. van Faassen,c   Gerard P. M. van Klink,ae   Martin Lutz,‡*b   John C. Chadwick,*de   Anthony L. Spek§b  and  Gerard van Koten*a  

* Corresponding authors

a Debye Institute for Nanomaterials Research, Organic Chemistry and Catalysis, Faculty of Science, Utrecht University, Padualaan 8, Utrecht, The Netherlands
E-mail: g.vankoten@uu.nl

b Bijvoet Center for Biomolecular Research, Crystal and Structural Chemistry, Faculty of Science, Utrecht University, Padualaan 8, Utrecht, The Netherlands

c Condensed Matter and Interfaces, Faculty of Science, Utrecht University, Padualaan 8, Utrecht, The Netherlands

d Laboratory of Polymer Chemistry, Eindhoven University of Technology, P.O. Box 513, Eindhoven, The Netherlands
E-mail: johnchad@xs4all.nl

e Dutch Polymer Institute, P.O. Box 902, Eindhoven, The Netherlands

Abstract

Transmetallation of 4,4′-bis{(2,6-bis[(dimethylamino)methyl]phenylgold)diphenyl-phosphino}biphenyl (3) with MCl4 (M = Ti, NbCl, V) in benzene gave the corresponding transition metal pincer complexes (4) and insoluble 4,4′-bis[P-(chloro gold(I))diphenylphosphino]biphenyl (2), which can be quantitatively recovered and recycled. Interestingly, 3 did not react with TiCl3. However, reaction of 2,6-bis[(dimethylamino)methyl]phenyllithium (1) with TiCl3 resulted in formation of the novel diaryltitanium(IV) compound 5 (16% yield), comprising one N,C,N-mer bound NCN-pincer ligand and a second NCN-pincer ligand that is rearranged from a 1,2,6-isomer to a 1,2,4 one. The latter NCN-ligand is dianionic and is bidentate bonded; one of the CH2NMe2 substituents (para to C′ipso) is non-coordinated, while the second CH2NMe2 group, after C–H activation of one of the Me groups, is η2-C,N-bonded to the titanium centre trans to Cipso of the mer-NCN ligand. The new NCN-pincer metal complexes 2,6-bis[(dimethylamino)methyl]phenylTiCl3 (4a) and 2,6-bis[(dimethylamino)methyl]-phenylVCl2 (4d) gave, after immobilization on MgCl2-based supports, very high activity in ethene polymerisation.

Graphical abstract: Mono N,C,N-pincer complexes of titanium, vanadium and niobium. Synthesis, structure and catalytic activity in olefin polymerisation

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Article information

DOI
https://doi.org/10.1039/C1DT10482A
Article type
Paper
Submitted
22 Mar 2011
Accepted
03 May 2011
First published
02 Jun 2011

Dalton Trans., 2011,40, 8887-8895

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Mono N,C,N-pincer complexes of titanium, vanadium and niobium. Synthesis, structure and catalytic activity in olefin polymerisation

A. V. Chuchuryukin, R. Huang, E. E. van Faassen, G. P. M. van Klink, M. Lutz, J. C. Chadwick, A. L. Spek and G. van Koten, Dalton Trans., 2011, 40, 8887 DOI: 10.1039/C1DT10482A

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