A DFT Study of the Hydroacylation Reaction Catalyzed by Rhodium Complexes with Small-Bite-Angle Diphosphine Ligands: The Crucial Role of External Lewis Bases
Andrew S. Weller, Michael C. Willis, Libero J. Bartolotti, Andrew T. Morehead Jr.* and Andrew L. Sargent*,
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引用次数: 0
Abstract
Hydroacylation catalysts have been previously reported [Chaplin, A. B.J. Am. Chem. Soc.2012, 134, 4885] that couple an alkene and a β-thioether aldehyde using cationic rhodium(I) catalysts with small-bite-angle diphosphine ligands. The higher catalytic activity was attributed to the facilitation of reductive elimination of the final product in the catalytic cycle, while external Lewis bases, including solvent (acetone and acetonitrile), were found to have a protective effect against catalyst deactivation. In this contribution, the relative energetics of these processes are examined computationally, and a unique role for the external Lewis base is discovered in which the base intercepts a critical intermediate in a pathway leading to catalyst deactivation and redirects the reaction to productive hydroacylation.
期刊介绍：
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.
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