DFT study of the reactivity of methane and dioxygen with d10-L2M complexes
A density functional theory analysis of the reactions of methane and O₂ with d¹⁰-L₂M complexes (M = Pd, Pt; L = N-heterocyclic carbene (NHC), PMe₃) is presented. Computations suggest that reaction of L₂M⁰ with O₂/CH₄ to form cis- (L)₂M(OOH)(CH₃) is only slightly uphill (ΔG ~ 10–11 kcal/mol). Based on calculated thermodynamics, reaction of (L)₂Pt⁰ with CH₄ and O₂ is predicted to be more favorable by first addition of CH₄ and then reaction of O₂ with the resulting methyl–hydrido complex. However, oxidative addition for either the C–H bond of methane or of O₂ to d¹⁰-L₂M complexes is kinetically prohibitive. If barriers to oxidative addition to d¹⁰-L₂M systems could be reduced, conversion of L₂M(H)(CH₃) to L₂M(OOH)(CH₃) via hydrogen atom abstract/radical rebound is calculated to be thermodynamically and kinetically feasible, particularly for NHC and Pd. As (NHC)₂Pd also has a lower free energy to methane C–H oxidative addition than does (NHC)₂Pt, the former combination would appear to be a promising starting point in the search for catalysts for partial hydrocarbon oxidation.
- Research Organization:
- Energy Frontier Research Centers (EFRC) (United States). Center for Catalytic Hydrocarbon Functionalization (CCHF)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- DOE Contract Number:
- SC0001298
- OSTI ID:
- 1065902
- Journal Information:
- Journal of Organometallic Chemistry, Vol. 696, Issue 25; Related Information: CCHF partners with University of Virginia (lead); Brigham Young University; California Institute of Technology; Colorado School of Mines; University of Maryland; University of North Carolina, Chapel Hill; University of North Texas; Princeton University; The Scripps Research Institute; Yale University
- Country of Publication:
- United States
- Language:
- English
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