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Rhodium Bis(quinolinyl)benzene Complexes for Methane Activation and Functionalization

Journal Article · · Chemistry - A European Journal
 [1];  [2];  [3];  [3];  [4]
  1. California Institute of Technology (CalTech), Pasadena, CA (United States); University of Virginia
  2. Univ. of Virginia, Charlottesville, VA (United States)
  3. California Institute of Technology (CalTech), Pasadena, CA (United States)
  4. Univ. of Virginia, Charlottesville, VA (United States); California Institute of Technology (CalTech), Pasadena, CA (United States)
+ Show Author Affiliations
A series of rhodium (III) bis(quinolinyl)benzene (bisqx) complexes was researched as candidates for the homogeneous partial oxidation of methane. Density functional theory (DFT) (M06 with Poisson continuum solvation) was used to investigate a variety of (bisqx) ligand candidates involving different functional groups to determine the impact on RhIII(bisqx) catalyzed methane functionalization. The free energy activation barriers for methane C–H activation and Rh–methyl functionalization at 298 K and 498 K were determined. DFT studies predict that the best candidate for catalytic methane functionalization is RhIII coordinated to unsubstituted bis(quinolinyl)benzene (bisq). Support is also found for the prediction that the η2-benzene coordination mode of (bisqx) ligands on Rh encourages methyl group functionalization by serving as an effective leaving group for SN2 and SR2 attack.
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:
1607784
Alternate ID(s):
OSTI ID: 1210265
OSTI ID: 1384689
Journal Information:
Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 3 Vol. 21; ISSN 0947-6539
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
C-H activation
ab initio calculations
catalysis
methane functionalization
rhodium