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DFT Virtual Screening Identifies Rhodium–Amidinate Complexes As Potential Homogeneous Catalysts for Methane-to-Methanol Oxidation

Journal Article · · ACS Catalysis
DOI:https://doi.org/10.1021/cs5005322· OSTI ID:1385891
 [1];  [1];  [1];  [2];  [2]
  1. Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125, United States
  2. Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, United States
+ Show Author Affiliations
In the search for new organometallic catalysts for low-temperature selective conversion of CH4 to CH3OH, we apply quantum mechanical virtual screening to select the optimum combination of ligand and solvent on rhodium to achieve low barriers for CH4 activation and functionalization to recommend for experimental validation. Here, we considered Rh because its lower electronegativity compared with Pt and Pd may allow it to avoid poisoning by coordinating media. We report quantum mechanical predictions (including implicit and explicit solvation) of the mechanisms for RhIII(NN) and RhIII(NNF) complexes [where (NN) = bis(N-phenyl)benzylamidinate and (NNF) = bis(N-pentafluorophenyl)pentafluorobenzylamidinate] to catalytically activate and functionalize methane using trifluoroacetic acid (TFAH) or water as a solvent. In particular, we designed the (NNF) ligand as a more electrophilic analogue to the (NN) ligand, and our results predict the lowest transition state barrier (ΔG‡ = 27.6 kcal/mol) for methane activation in TFAH from a pool of four different classes of ligands. To close the catalytic cycle, the functionalization of methylrhodium intermediates was also investigated, involving carbon–oxygen bond formation via SN2 attack by solvent, or SR2 attack by a vanadium oxo. Activation barriers for the functionalization of methylrhodium intermediates via nucleophilic attack are lower when the solvent is water, but CH4 activation barriers are higher. In addition, we have found a correlation between CH4 activation barriers and rhodium–methyl bond energies that allow us to predict the activation transition state energies for future ligands, as well.
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) (SC-22)
DOE Contract Number:
SC0001298
OSTI ID:
1385891
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 12 Vol. 4; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

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Quasicatalytic and catalytic selective oxidation of methane to methanol over solid materials: a review on the roles of water journal October 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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