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. Faassen, van, G.P.M. Klink, van, M. Lutz, J.C. Chadwick, A.L. Spek, G. Koten, van

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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 ¿2-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.
Original languageEnglish
Pages (from-to)8887-8895
JournalDalton Transactions
Volume40
Issue number35
DOIs
Publication statusPublished - 2011

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    Chuchuryukin, A. V., Huang, R., Faassen, van, E. E., Klink, van, G. P. M., Lutz, M., Chadwick, J. C., Spek, A. L., & Koten, van, G. (2011). Mono N,C,N-pincer complexes of titanium, vanadium and niobium. Synthesis, structure and catalytic activity in olefin polymerisation. Dalton Transactions, 40(35), 8887-8895. https://doi.org/10.1039/c1dt10482a