Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published November 11, 2014 | Supplemental Material
Journal Article Open

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

Abstract

In the search for new organometallic catalysts for low-temperature selective conversion of CH_4 to CH_3OH, we apply quantum mechanical virtual screening to select the optimum combination of ligand and solvent on rhodium to achieve low barriers for CH_4 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 Rh^(III)(NN) and Rh^(III)(NN^F) complexes [where (NN) = bis(N-phenyl)benzylamidinate and (NN^F) = bis(N-pentafluorophenyl)pentafluorobenzylamidinate] to catalytically activate and functionalize methane using trifluoroacetic acid (TFAH) or water as a solvent. In particular, we designed the (NN^F) 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 S_N2 attack by solvent, or S_R2 attack by a vanadium oxo. Activation barriers for the functionalization of methylrhodium intermediates via nucleophilic attack are lower when the solvent is water, but CH_4 activation barriers are higher. In addition, we have found a correlation between CH_4 activation barriers and rhodium–methyl bond energies that allow us to predict the activation transition state energies for future ligands, as well.

Additional Information

© 2014 American Chemical Society. Received: April 21, 2014, Revised: August 26, 2014, Publication Date (Web): October 20, 2014. This work was supported as part of the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DOE DE-SC0001298.

Attached Files

Supplemental Material - cs5005322_si_001.pdf

Supplemental Material - cs5005322_si_002.pdf

Files

cs5005322_si_002.pdf
Files (7.2 MB)
Name Size Download all
md5:18921ef9097cf89df2ac6c41f7ac015a
5.7 MB Preview Download
md5:ecac9934f2b1bc29d57fbc303ce60d88
1.5 MB Preview Download

Additional details

Created:
August 22, 2023
Modified:
October 18, 2023