Issue 25, 2013

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

Abstract

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 phenoxy-imine (3-(t-butyl)-2-(OH)-C6H4C[double bond, length as m-dash]N(C(CH3)2CH2OMe) 1, 3-(adamantyl)-2-(OH)-C6H4C[double bond, length as m-dash]N(2′-(2′′-(SMe)C6H4)-C6H4) 2, 3-(t-butyl)-2-(OSiMe3)-C6H4C[double bond, length as m-dash]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 phenoxy-imine 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.

Graphical abstract: Synthesis of Ti(iv) complexes of donor-functionalised phenoxy-imine tridentates and their evaluation in ethylene oligomerisation and polymerisation

Supplementary files

Article information

Article type
Paper
Submitted
17 Oct 2012
Accepted
29 Jan 2013
First published
29 Jan 2013

Dalton Trans., 2013,42, 9129-9138

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

J. A. Suttil, M. F. Shaw, D. S. McGuinness, M. G. Gardiner and S. J. Evans, Dalton Trans., 2013, 42, 9129 DOI: 10.1039/C3DT32465F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements