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.
authors.affiliation: Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK. did3@leicester.ac.uk
authors.forename: David L
authors.initials: DL
authors.lastname: Davies
authors.forename: Steven M A
authors.initials: SM
authors.lastname: Donald
authors.forename: Stuart A
authors.initials: SA
authors.lastname: Macgregor
mesh_terms: D000085:Acetates / Q000737:chemistry*; D003198:Computer Simulation; D018360:Crystallography, X-Ray; D003500:Cyclization; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*
chemical_list: D000085:Acetates; D009942:Organometallic Compounds; D010165:Palladium