期刊
ORGANOMETALLICS
卷 40, 期 24, 页码 4120-4132出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.1c00574
关键词
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资金
- US National Science Foundation [CHE-1856416]
- Ministerio de Educacion, Cultura y Deporte, Programa Estatal de Promocion del Talento y su Empleabilidad en I+D+i, Subprograma Estatal de Movilidad del Plan Estatal de I+D+I [PRX19/00533]
- US National Science Foundation (XSEDE)
Density functional theory calculations were used to investigate the effects of axial ligation by solvent molecules on reactivity and selectivity of dirhodium tetracarboxylates with diazo compounds in C-H insertion reactions. The results suggest that axial ligation significantly influences the barriers for N-2 extrusion and C-H insertion, with a greater impact on the former.
Density functional theory calculations were used to systematically explore the effects of axial ligation by solvent molecules on the reactivity and selectivity of dirhodium tetracarboxylates with diazo compounds in the context of C-H insertion into propane. Insertions on three types of diazo compounds-acceptor/acceptor, donor/acceptor, and donor/donor-promoted by dirhodium tetraformate were tested with and without axial solvent ligation for no surrounding solvent, dichloromethane, isopropanol, and acetonitrile. Magnitudes, origins, and consequences of structural and electronic changes arising from axial ligation were characterized. The results suggest that axial ligation affects barriers for N-2 extrusion and C-H insertion, the former to a larger extent.
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