THEORETICAL-STUDIES OF INORGANIC AND ORGANOMETALLIC REACTION-MECHANISMS .6. METHANE ACTIVATION ON TRANSIENT CYCLOPENTADIENYLCARBONYLRHODIUM

abstract

• The C-H oxidative-addition of methane to the transient RhCp(CO) complex was studied with ab initio RHF and MP2 techniques. Electron correlation dramatically alters the reaction energetics and shifts the intermediate later and the transition state earlier in the reaction coordinate. The MP2 calculations predict an intermediate stabilized by 14.8 kcal/mol, a transition state with an activation barrier of 4.1 kcal/mol relative to the intermediate, and a reaction product exothermic by 30.6 kcal/mol. Analyses of the molecular structure and the Laplacian of the total charge density reveal an agostic-like intermediate with metal-CH dative interaction in the early stage of the reaction. The transition state shows obvious C-H bond breaking and is significantly stabilized by newly forming Rh-C and Rh-H bonding interactions. 1993, American Chemical Society. All rights reserved.

authors

• Hall, Michael

published proceedings

• ORGANOMETALLICS

author list (cited authors)

• SONG, J., & HALL, M. B.

citation count

• 73

complete list of authors

• SONG, J||HALL, MB

publication date

• August 1993

publisher

• American Chemical Society (ACS)  Publisher

published in

• Organometallics  Journal

keywords

• 34 Chemical Sciences
• 3407 Theoretical And Computational Chemistry

Digital Object Identifier (DOI)

• 10.1021/om00032a039

start page

• 3118

end page

• 3126

volume

• 12

issue

• 8

URL

• https://doi.org/10.1021/om00032a039