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DOI	10.1073/pnas.1816339116
	Polar molecules catalyze CO insertion into metal-alkyl bonds through the displacement of an agostic C-H bond
	Zhou T.; Malakar S.; Webb S.L.; Krogh-Jespersen K.; Goldman A.S.
发表日期	2019
ISSN	0027-8424
起始页码	3419
结束页码	3424
卷号	116 期号:9
英文摘要	The insertion of CO into metal-alkyl bonds is the key C-C bond-forming step in many of the most important organic reactions catalyzed by transition metal complexes. Polar organic molecules (e.g., tetrahydrofuran) have long been known to promote CO insertion reactions, but the mechanism of their action has been the subject of unresolved speculation for over five decades. Comprehensive computational studies [density functional theory (DFT)] on the prototypical system Mn(CO)5(arylmethyl) reveal that the polar molecules do not promote the actual alkyl migration step. Instead, CO insertion (i.e. alkyl migration) occurs rapidly and reversibly to give an acyl complex with a sigma-bound (agostic) C-H bond that is not easily displaced by typical ligands (e.g. phosphines or CO). The agostic C-H bond is displaced much more readily, however, by the polar promoter molecules, even though such species bind only weakly to the metal center and are themselves then easily displaced; the facile kinetics of this process are attributable to a hydrogen bonding-like interaction between the agostic C-H bond and the polar promoter. The role of the promoter is to thereby catalyze isomerization of the agostic product of CO insertion to give an η2-C,O-bound acyl product that is more easily trapped than the agostic species. This ability of such promoters to displace a strongly sigma-bound C-H bond and to subsequently undergo facile displacement themselves is without reported precedent, and could have implications for catalytic reactions beyond carbonylation. © 2019 National Academy of Sciences. All Rights Reserved.
英文关键词	Agostic; Carbonylation; Catalysis; CO insertion; Hydrogen bonding
语种	英语
scopus关键词	acyl derivative; carbon; carbon monoxide; chemical compound; hydrogen; polar organic molecule; unclassified drug; Article; carbon hydrogen bond; carbon monoxide insertion; carbonylation; catalysis; chemical binding; chemical bond; chemical interaction; chemical structure; density functional theory; hydrogen bond; isomerization; kinetics; ligand binding; mathematical model; metal alkyl bond; migration; nucleophilicity; priority journal
来源期刊	Proceedings of the National Academy of Sciences of the United States of America
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/160373
作者单位	Zhou, T., Department of Chemistry and Chemical Biology, Rutgers, State University of New Jersey, New Brunswick, NJ 08903, United States; Malakar, S., Department of Chemistry and Chemical Biology, Rutgers, State University of New Jersey, New Brunswick, NJ 08903, United States; Webb, S.L., Department of Chemistry, University of Chicago, Chicago, IL 60637, United States; Krogh-Jespersen, K., Department of Chemistry and Chemical Biology, Rutgers, State University of New Jersey, New Brunswick, NJ 08903, United States; Goldman, A.S., Department of Chemistry and Chemical Biology, Rutgers, State University of New Jersey, New Brunswick, NJ 08903, United States
推荐引用方式 GB/T 7714	Zhou T.,Malakar S.,Webb S.L.,et al. Polar molecules catalyze CO insertion into metal-alkyl bonds through the displacement of an agostic C-H bond[J],2019,116(9).
APA	Zhou T.,Malakar S.,Webb S.L.,Krogh-Jespersen K.,&Goldman A.S..(2019).Polar molecules catalyze CO insertion into metal-alkyl bonds through the displacement of an agostic C-H bond.Proceedings of the National Academy of Sciences of the United States of America,116(9).
MLA	Zhou T.,et al."Polar molecules catalyze CO insertion into metal-alkyl bonds through the displacement of an agostic C-H bond".Proceedings of the National Academy of Sciences of the United States of America 116.9(2019).