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Synthesis of Ti(IV) complexes of donor-functionalised phenoxy-imine tridentates and their evaluation in ethylene oligomerisation and polymerisation

journal contribution
posted on 2023-05-17, 21:30 authored by Suttil, JA, Shaw, MF, McGuinness, DS, Michael GardinerMichael Gardiner, Evans, SJ
A number of analogues of the Mitsui Chemicals ethylene trimerisation system (IV) have been explored, in which one of the donor atoms have been modified. Thus, a series of mono-anionic tridentate phenoxyimine (3-(t-butyl)-2-(OH)-C6H4C=N(C(CH3)2CH2OMe) 1, 3-(adamantyl)-2-(OH)-C6H4C=N(2’-(2’’-(SMe)- C6H4)-C6H4) 2, 3-(t-butyl)-2-(OSiMe3)-C6H4C=N(C(CH3)2CH2OMe) 3) or phenoxy-amine (3,5-di(t-butyl)-2-(OH)-C6H4CH2-N(2’-(2’’-(OMe)C6H4)-C6H4) 4) ligands have been prepared and reacted with TiCl4 or TiCl4(thf)2 to give the mono-ligand complexes 5–7. The solid state structures of compounds 4–6 have been determined. Complexes 5–7 have been tested for their potential as ethylene oligomerisation/polymerisation systems in conjunction with MAO activator and benchmarked against the Mitsui phenoxyimine trimerisation system IV. While the phenoxy-amine complex 6 shows a propensity for polymer formation, the phenoxy-imine complexes 5 and 7 show somewhat increased formation of short chain LAOs. Complex 5 is selective for 1-butene in the oligomeric fraction, while 7 displays liquid phase selectivity to 1-hexene. As such 7, which is a sulfur substituted analogue of the Mitsui system IV, displays similar characteristics to the parent catalyst. However, its utility is limited by the lower activity and predominant formation of polyethylene.

Funding

Sasol Technology Pty Ltd

History

Publication title

Dalton Transactions: the international journal for inorganic, organometallic and bioinorganic chemistry

Volume

42

Issue

25

Pagination

9129-9138

ISSN

1477-9226

Department/School

School of Natural Sciences

Publisher

RSC Publications

Place of publication

United Kingdom

Rights statement

Copyright 2013 Dalton Transactions

Repository Status

  • Restricted

Socio-economic Objectives

Organic industrial chemicals (excl. resins, rubber and plastics)

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    University Of Tasmania

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