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

Abstract

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.

Authors:
 [1];  [2];  [1];  [1];  [3]
+ Show Author Affiliations
  1. California Institute of Technology (CalTech), Pasadena, CA (United States)
  2. Univ. of Virginia, Charlottesville, VA (United States)
  3. Univ. of Virginia, Charlottesville, VA (United States); California Institute of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
Univ. of Virginia, Charlottesville, VA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1607784
Grant/Contract Number:  
SC0001298
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 21; Journal Issue: 3; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ab initio calculations; catalysis; C-H activation; methane functionalization; rhodium

Citation Formats

Fu, Ross, O'Reilly, Matthew E., Nielsen, Robert J., Goddard III , William A., and Gunnoe, T. Brent. Rhodium Bis(quinolinyl)benzene Complexes for Methane Activation and Functionalization. United States: N. p., 2014. Web. doi:10.1002/chem.201405460.
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Fu, Ross, O'Reilly, Matthew E., Nielsen, Robert J., Goddard III , William A., & Gunnoe, T. Brent. Rhodium Bis(quinolinyl)benzene Complexes for Methane Activation and Functionalization. United States. https://doi.org/10.1002/chem.201405460
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Fu, Ross, O'Reilly, Matthew E., Nielsen, Robert J., Goddard III , William A., and Gunnoe, T. Brent. Fri . "Rhodium Bis(quinolinyl)benzene Complexes for Methane Activation and Functionalization". United States. https://doi.org/10.1002/chem.201405460. https://www.osti.gov/servlets/purl/1607784.
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@article{osti_1607784,
title = {Rhodium Bis(quinolinyl)benzene Complexes for Methane Activation and Functionalization},
author = {Fu, Ross and O'Reilly, Matthew E. and Nielsen, Robert J. and Goddard III , William A. and Gunnoe, T. Brent},
abstractNote = {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.},
doi = {10.1002/chem.201405460},
journal = {Chemistry - A European Journal},
number = 3,
volume = 21,
place = {United States},
year = {Fri Nov 21 00:00:00 EST 2014},
month = {Fri Nov 21 00:00:00 EST 2014}
}
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https://doi.org/10.1002/chem.201405460
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    The Direct Catalytic Oxidation of Methane to Methanol-A Critical Assessment
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