Computational study of the mechanism of cyclometalation by palladium acetate

David L. Davies; S. M A Donald; Stuart A. Macgregor

doi:10.1021/ja052047w

Computational study of the mechanism of cyclometalation by palladium acetate

David L. Davies, S. M A Donald, Stuart A. Macgregor

School of Engineering & Physical Sciences

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658 Citations (Scopus)

Abstract

Various mechanisms for the cyclometalation of dimethylbenzylamine by palladium acetate have been studied by DFT calculations. Contrary to previous suggestions, the rate-limiting step is the electrophilic attack of the palladium on an ortho arene C-H bond to form an agostic complex rather than a Wheland intermediate. The cyclometalated product is then formed by intramolecular deprotonation by acetate via a six-membered transition state; this step has almost no activation barrier. Copyright © 2005 American Chemical Society.

Original language	English
Pages (from-to)	13754-13755
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	127
Issue number	40
DOIs	https://doi.org/10.1021/ja052047w
Publication status	Published - 12 Oct 2005

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abstract = "Various mechanisms for the cyclometalation of dimethylbenzylamine by palladium acetate have been studied by DFT calculations. Contrary to previous suggestions, the rate-limiting step is the electrophilic attack of the palladium on an ortho arene C-H bond to form an agostic complex rather than a Wheland intermediate. The cyclometalated product is then formed by intramolecular deprotonation by acetate via a six-membered transition state; this step has almost no activation barrier. Copyright {\textcopyright} 2005 American Chemical Society.",

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N2 - Various mechanisms for the cyclometalation of dimethylbenzylamine by palladium acetate have been studied by DFT calculations. Contrary to previous suggestions, the rate-limiting step is the electrophilic attack of the palladium on an ortho arene C-H bond to form an agostic complex rather than a Wheland intermediate. The cyclometalated product is then formed by intramolecular deprotonation by acetate via a six-membered transition state; this step has almost no activation barrier. Copyright © 2005 American Chemical Society.

AB - Various mechanisms for the cyclometalation of dimethylbenzylamine by palladium acetate have been studied by DFT calculations. Contrary to previous suggestions, the rate-limiting step is the electrophilic attack of the palladium on an ortho arene C-H bond to form an agostic complex rather than a Wheland intermediate. The cyclometalated product is then formed by intramolecular deprotonation by acetate via a six-membered transition state; this step has almost no activation barrier. Copyright © 2005 American Chemical Society.

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Computational study of the mechanism of cyclometalation by palladium acetate

Abstract

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