The mechanism for the polymerization of ethylene via a mononuclear aluminum catalyst has been shown previously to lead to inconsistent results. We propose here for the first time a plausible mechanism involving a dinuclear aluminum species which overcomes the problems of the mononuclear catalyst. With the aid of computational quantum chemistry, we have shown that the dinuclear pathway has a much lower activation energy than the mononuclear pathway, a result which can be explained in terms of a greater orbital overlap being maintained in the dinuclear transition structure. We show that the generation of one growing polymer chain is more likely than that of two or three growing polymer chains. Importantly we find that the propagation step is more favorable than termination, which is in contrast to the findings with the mononuclear catalyst. © 2013 American Chemical Society.

Item Type:	Refereed Article
Keywords:	ethylene polymerization, aluminum complex
Research Division:	Chemical Sciences
Research Group:	Other Chemical Sciences
Research Field:	Organometallic Chemistry
Objective Division:	Expanding Knowledge
Objective Group:	Expanding Knowledge
Objective Field:	Expanding Knowledge in the Chemical Sciences
UTAS Author:	Yates, BF (Professor Brian Yates)
UTAS Author:	Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:	89244
Year Published:	2013
Web of Science® Times Cited:	4
Deposited By:	Chemistry
Deposited On:	2014-02-27
Last Modified:	2015-01-21
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