Computational Study of the Mechanism of Cyclometalation by Palladium Acetate

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 Whel...

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Veröffentlicht in:	Journal of the American Chemical Society 2005-10, Vol.127 (40), p.13754-13755
Hauptverfasser:	Davies, David L, Donald, Steven M. A, Macgregor, Stuart A
Format:	Artikel
Sprache:	eng
Schlagworte:	Acetates - chemistry Chemistry Computer Simulation Crystallography, X-Ray Cyclization Exact sciences and technology Kinetics and mechanisms Models, Molecular Molecular Structure Organic chemistry Organometallic Compounds - chemical synthesis Organometallic Compounds - chemistry Palladium - chemistry Reactivity and mechanisms
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Beschreibung
Zusammenfassung:	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.
ISSN:	0002-7863 1520-5126
DOI:	10.1021/ja052047w