Participation of Carbonyl Oxygen in Carbon鈥揅arboxylate Bond-Forming Reductive Elimination from Palladium

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• 作者：J. Brannon Gary ; Melanie S. Sanford
• 刊名：Organometallics
• 出版年：2011
• 出版时间：November 28, 2011
• 年：2011
• 卷：30
• 期：22
• 页码：6143-6149
• 全文大小：931K
• 年卷期：v.30,no.22(November 28, 2011)
• ISSN：1520-6041

文摘

This paper describes density functional theory (DFT) calculations of the mechanism of carbon-acetate bond-forming reductive elimination from Pd centers. This C鈥揙 coupling reaction has been studied at a series of different Pd^IV, Pd^III, and Pd^II complexes. In all cases, three-membered transition states involving direct coupling of the Pd-bound O and C atoms have been compared to five-membered transition states where the pendant carbonyl oxygen participates in the C鈥揙 coupling event. These calculations show that the five-membered transition state is kinetically favored by between 4.7 and 13.2 kcal/mol.