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Issue 41, 2009
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DFT investigation of the ‘quasi-living’ propene polymerisation with Cp*TiMe3/B(C6F5)3: the ‘naked cation’ approach

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Abstract

Some time ago we reported the quasi-living polymerization of propene with the catalytic mixture of Cp*TiMe3 and B(C6F5)3 (Cp* = C5Me5). Surprisingly, this mixture is extremely sensitive towards the nature of the anion and the presence of aluminium alkyl. This intriguing observation led us to the attempt to unearth the underlying reaction mechanism using a computational approach. In this communication, we are reporting the first results with the ‘naked cation’ approach. We obtained evidence, that the 1,2 insertion is the predominant reaction pathway. Whereas initial 1,2 and 2,1 insertion barriers are comparable, consequent second insertion is more discriminating between the two. Although we obtained evidence for the formation of β-H agostic bonds, we found that β-H elimination is a rare event due to the rather high activation barrier. We can conclude that the quasi-living polymerisation is at least partly an intrinsic property of the cation.

Graphical abstract: DFT investigation of the ‘quasi-living’ propene polymerisation with Cp*TiMe3/B(C6F5)3: the ‘naked cation’ approach

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Publication details

The article was received on 26 May 2009, accepted on 07 Aug 2009 and first published on 20 Aug 2009


Article type: Paper
DOI: 10.1039/B910339B
Citation: Dalton Trans., 2009,0, 8993-8999
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    DFT investigation of the ‘quasi-living’ propene polymerisation with Cp*TiMe3/B(C6F5)3: the ‘naked cation’ approach

    J. Saßmannshausen, Dalton Trans., 2009, 0, 8993
    DOI: 10.1039/B910339B

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