Computational Study of the Mechanism of Cyclometalation by Palladium Acetate
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- 17 September 2005
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 127 (40) , 13754-13755
- https://doi.org/10.1021/ja052047w
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.Keywords
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