Computational Study of the Mechanism of Cyclometalation by Palladium Acetate

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2005 Oct 6

PMID 16201772

Citations 82

Authors

David L Davies

Steven M A Donald

Stuart A Macgregor

Affiliations

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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.

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