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Theoretical investigation into the mechanism of ethylene polymerization by a cationic dinuclear aluminum complex: a longstanding unresolved issue
journal contribution
posted on 2023-05-17, 22:41 authored by Ghorbani, N, Mahdizadeh Ghohe, N, Torabi, S, Brian YatesBrian Yates, Alireza AriafardAlireza AriafardThe 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.
History
Publication title
OrganometallicsVolume
32Issue
6Pagination
1687-1693ISSN
0276-7333Department/School
School of Natural SciencesPublisher
American Chemical SocietyPlace of publication
1155 16Th St, Nw, Washington, USA, Dc, 20036Rights statement
Copyright 2013 American Chemical SocietyRepository Status
- Restricted