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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:1607792
 [1];  [2];  [2];  [3];  [3]
  1. California Institute of Technology (CalTech), Pasadena, CA (United States); University of Virginia
  2. California Institute of Technology (CalTech), Pasadena, CA (United States)
  3. Univ. of Virginia, Charlottesville, VA (United States)
+ Show Author Affiliations
In our research 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 since its lower electronegativity compared to Pt and Pd may allow it to avoid poisoning by coordinating media. We report here 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 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:
Univ. of Virginia, Charlottesville, VA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0001298
OSTI ID:
1607792
Alternate ID(s):
OSTI ID: 1210864
OSTI ID: 1385891
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 12 Vol. 4; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
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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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
C−H activation
amidinate
catalysis
fluorinated ligands
methane functionalization
quantum mechanical screening
rhodium