Computational study of the mechanism of cyclometalation by palladium acetate

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

doi:10.1021/ja052047w

Computational study of the mechanism of cyclometalation by palladium acetate

David L. Davies^*, Steven M.A. Donald, Stuart A. Macgregor

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article › peer-review

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.

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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title = "Computational study of the mechanism of cyclometalation by palladium acetate",

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.",

author = "Davies, \{David L.\} and Donald, \{Steven M.A.\} and Macgregor, \{Stuart A.\}",

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AU - Davies, David L.

AU - Donald, Steven M.A.

AU - Macgregor, Stuart A.

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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.

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.

UR - https://www.scopus.com/pages/publications/26444441381

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DO - 10.1021/ja052047w

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AN - SCOPUS:26444441381

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SP - 13754

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 40

ER -

Computational study of the mechanism of cyclometalation by palladium acetate

Abstract

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