Issue 3, 2001
From the journal:

Journal of the Chemical Society, Dalton Transactions

2-tert-Butyl and 2-phenylphenylimido complexes of titanium(IV) and their olefinpolymerisation activity

Alastair J. Nielson,*a   Mark W. Glennyb  and  Clifton E. F. Rickardb  

* Corresponding authors

a Chemistry, Institute of Fundamental Sciences, Massey University at Albany, Private Bag 102904, North Shore Mail Centre, Auckland, New Zealand

b Department of Chemistry, The University of Auckland, Private Bag 92019, Auckland, New Zealand

Abstract

Reaction of 7 equivalents of tert-butylamine with TiCl4 in hexane at 0 °C gave [TiCl2(NCMe3)(NH2CMe3)2]21 which on thermalisation with 2,6-diisopropylaniline in toluene gave [TiCl2(NC6H3Pri2-2,6)(NH2CMe3)2]x2. Imido exchange of [TiCl2(NCMe3)(NH2CMe3)]x with o-toluidine or 2-tert-butylaniline and addition of pyridine gave [TiCl2(NC6H4Me-2)(py)3] and [TiCl2(NC6H4CMe3-2)(py)3] which crystallised to give [TiCl2(NC6H4Me-2)(py)2]23 and [TiCl2(NC6H4CMe3-2)(py)2]24. 2-Phenylaniline and [TiCl2(NCMe3)(py)3] gave [TiCl2(NC6H4Ph-2)(py)2]25 on crystallisation and reaction of tert-butylaniline or 2-phenylaniline with [TiCl2(NCMe3)(tmeda)] gave [TiCl2(NC6H4CMe3-2)(tmeda)] 6 and [TiCl2(NC6H4Ph-2)(tmeda)]27. Complexes 1, 3, 4, 5, 6, and 7 were characterised by X-ray crystallography and the possibility of imdo ligand C–N bond rotation taking place analysed and compared with the NMR spectra. [TiCl2(NCMe3)(tmeda)] and MAO·(MeAlO)n, polymerises ethylene at low pressure with low activity (3.2 g mmol−1 h−1 bar−1), [TiCl2(NC6H4CMe3)(tmeda)] or [TiCl2(NC6H4Ph-2)(tmeda)] and MAO gives a 4-fold increase in activity whereas propene is not polymerised but 1-hexene is. Heterogenisation by addition of [TiCl2(NCMe3)(NH2CMe3)2]21 to tmeda-functionalised crosslinked polystyrene or imido exchange of [TiCl2(NCMe3)(tmeda)] with NH2-functionalised crosslinked polystyrene gives supported complexes which do not polymerise ethylene at low pressure in the presence of MAO.

Graphical abstract: 2-tert-Butyl and 2-phenylphenylimido complexes of titanium(IV) and their olefin polymerisation activity

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Article information

DOI
https://doi.org/10.1039/B008232P
Article type
Paper
Submitted
12 Oct 2000
Accepted
20 Nov 2000
First published
15 Jan 2001

J. Chem. Soc., Dalton Trans., 2001, 232-239

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2-tert-Butyl and 2-phenylphenylimido complexes of titanium(IV) and their olefin polymerisation activity

A. J. Nielson, M. W. Glenny and C. E. F. Rickard, J. Chem. Soc., Dalton Trans., 2001, 232 DOI: 10.1039/B008232P

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