Theoretical studies of inorganic and organometallic reaction mechanisms. 6. Methane activation on transient cyclopentadienylcarbonylrhodium
- Texas A M Univ., College Station (United States)
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. 26 refs., 9 figs., 3 tabs.
- OSTI ID:
- 5746759
- Journal Information:
- Organometallics; (United States), Vol. 12:8; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
METHANE
CHEMICAL ACTIVATION
REACTION INTERMEDIATES
MOLECULAR STRUCTURE
THERMODYNAMICS
EXPERIMENTAL DATA
HARTREE-FOCK METHOD
ORGANOMETALLIC COMPOUNDS
RHODIUM COMPLEXES
ALKANES
CALCULATION METHODS
COMPLEXES
DATA
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
TRANSITION ELEMENT COMPLEXES
030400* - Natural Gas- Products & By-Products
400201 - Chemical & Physicochemical Properties