The synthesis, structure and ethene polymerisation catalysis of mono(salicylaldiminato) titanium and zirconium complexes

D. A. Pennington, W. Clegg, S. J. Coles, R. W. Harrington, M. B. Hursthouse, D. L. Hughes, M. E. Light, M. Schormann, M. Bochmann, S. J. Lancaster

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Abstract

The silyl ethers 3- Bu-t - 2- ( OSiMe3) C6H3CH = NR ( 2a- e) have been prepared by deprotonation of the known iminophenols ( 1a - e) and treatment with SiClMe3 ( a, R = C6H5; b, R = 2,6- Pr-i 2C6H3; c, R = 2,4,6- Me3C6H2; d, R = 2- C6H5C6H4; e, R = C6F5). 2a - c react with TiCl4 in hydrocarbon solvents to give the binuclear complexes [ Ti {3- Bu-t - 2-( O) C6H3CH = N( R)} Cl( mu - Cl-3) TiCl3] ( 3a - c). The pentafluorophenyl species 2e reacts with TiCl4 to give the known complex Ti {3- Bu-t - 2- ( O) C6H3CH = N( R)} Cl-2(2). The mononuclear five- coordinate complex, Ti {3- Bu-t - 2- ( O) C6H3CH = N( 2,4,6- Me3C6H2)} Cl-3 ( 4c), was isolated after repeated recrystallisation of 3c. Performing the dehalosilylation reaction in the presence of tetrahydrofuran yields the octahedral, mononuclear complexes Ti {3- Bu-t - 2- ( O) C6H3CH = N( R)} Cl-3( THF) ( 5a - e). The reaction with ZrCl4( THF) (2) proceeds similarly to give complexes Zr {3- Bu-t - 2- ( O) C6H3CH = N( R)} Cl-3( THF) ( 6b - e). The crystal structures of 3b, 4c, 5a, 5c, 5e, 6b, 6d, 6e and the salicylaldehyde titanium complex Ti {3- Bu-t - 2- ( O) C6H3CH = O} Cl-3( THF) ( 7) have been determined. Activation of complexes 5a e and 6b e with MAO in an ethene saturated toluene solution gives polyethylene with at best high activity depending on the imine substituent.
Original languageEnglish
Pages (from-to)561-571
Number of pages11
JournalDalton Transactions
Issue number3
DOIs
Publication statusPublished - 2005

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