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

Fu, Ross; O'Reilly, Matthew E.; Nielsen, Robert J; Goddard, III, William A.; Gunnoe, T. Brent

doi:10.1002/chem.201405460

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

Authors:: Fu, Ross; O'Reilly, Matthew E.; Nielsen, Robert J; Goddard, III, William A.; Gunnoe, T. Brent

Publication Date:: Fri Nov 21 00:00:00 EST 2014

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Center for Catalytic Hydrocarbon Functionalization (CCHF)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1210265

DOE Contract Number:: SC0001298

Resource Type:: Journal Article

Journal Name:: Chem. Eur. J.

Additional Journal Information:: Journal Volume: 21; Related Information: CCHF partners with University of Virginia (lead); Brigham Young University; California Institute of Technology; Colorado School of Mines; University of Maryland; University of North Carolina, Chapel Hill; University of North Texas; Princeton University; The Scripps Research Institute; Yale University

Country of Publication:: United States

Language:: English

Subject:: catalysis (homogeneous), catalysis (heterogeneous), bio-inspired, hydrogen and fuel cells, materials and chemistry by design, synthesis (novel materials)

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.

Copy to clipboard


                    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

Copy to clipboard


                    Fu, Ross, O'Reilly, Matthew E., Nielsen, Robert J, Goddard, III, William A., and Gunnoe, T. Brent. 2014.  
        "Rhodium Bis(quinolinyl)benzene Complexes for Methane Activation and Functionalization".  United States.  https://doi.org/10.1002/chem.201405460.

Copy to clipboard


                    
@article{osti_1210265,

  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 = {},

  doi          = {10.1002/chem.201405460},

  url          = {https://www.osti.gov/biblio/1210265},
  journal      = {Chem. Eur. J.},
number       = ,

  volume       = 21,

  place        = {United States},

  year         = {Fri Nov 21 00:00:00 EST 2014},

  month        = {Fri Nov 21 00:00:00 EST 2014}

}

Copy to clipboard

Journal Article:

https://doi.org/10.1002/chem.201405460

Other availability

Find in Google Scholar

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Understanding and exploiting C–H bond activation
journal, May 2002

Labinger, Jay A.; Bercaw, John E.
Nature, Vol. 417, Issue 6888
https://doi.org/10.1038/417507a

Alkane C–H activation and functionalization with homogeneous transition metal catalysts: a century of progress—a new millennium in prospect
journal, January 2001

Crabtree, Robert H.
Journal of the Chemical Society, Dalton Transactions, Issue 17
https://doi.org/10.1039/b103147n

Methane activation in homogeneous systems
journal, April 1995

Labinger, Jay A.
Fuel Processing Technology, Vol. 42, Issue 2-3
https://doi.org/10.1016/0378-3820(94)00107-5

Selective alkane oxidation: hot and cold approaches to a hot problem
journal, September 2004

Labinger, Jay A.
Journal of Molecular Catalysis A: Chemical, Vol. 220, Issue 1
https://doi.org/10.1016/j.molcata.2004.03.051

A Mercury-Catalyzed, High-Yield System for the Oxidation of Methane to Methanol
journal, January 1993

Periana, R. A.; Taube, D. J.; Evitt, E. R.
Science, Vol. 259, Issue 5093
https://doi.org/10.1126/science.259.5093.340

New Catalyst Systems for the Catalytic Conversion of Methane into Methanol
journal, May 2002

Muehlhofer, Michael; Strassner, Thomas; Herrmann, Wolfgang A.
Angewandte Chemie International Edition, Vol. 41, Issue 10
https://doi.org/10.1002/1521-3773(20020517)41:10<1745::AID-ANIE1745>3.0.CO;2-E

Neue Katalysatorsysteme für die katalytische Oxidation von Methan zu Methanol
journal, May 2002

Muehlhofer, Michael; Strassner, Thomas; Herrmann, Wolfgang A.
Angewandte Chemie, Vol. 114, Issue 10
https://doi.org/10.1002/1521-3757(20020517)114:10<1817::AID-ANGE1817>3.0.CO;2-4

Activation of Methane and Ethane and Their Selective Oxidation to the Alcohols in Protic Media
journal, February 1994

Sen, Ayusman; Benvenuto, Mark A.; Lin, Minren
Journal of the American Chemical Society, Vol. 116, Issue 3
https://doi.org/10.1021/ja00082a022

Selective Intermolecular Carbon-Hydrogen Bond Activation by Synthetic Metal Complexes in Homogeneous Solution
journal, March 1995

Arndtsen, Bruce A.; Bergman, Robert G.; Mobley, T. Andrew
Accounts of Chemical Research, Vol. 28, Issue 3
https://doi.org/10.1021/ar00051a009

Alkane C−H Activation and Catalysis by an O-Donor Ligated Iridium Complex
journal, November 2003

Wong-Foy, Antek G.; Bhalla, Gaurav; Liu, Xiang Yang
Journal of the American Chemical Society, Vol. 125, Issue 47
https://doi.org/10.1021/ja037849a

Mechanism of Homogeneous Ir(III) Catalyzed Regioselective Arylation of Olefins
journal, January 2004

Oxgaard, Jonas; Muller, Richard P.; Goddard, William A.
Journal of the American Chemical Society, Vol. 126, Issue 1
https://doi.org/10.1021/ja034126i

Synthesis, Structure, and Reactivity of O-Donor Ir(III) Complexes: C−H Activation Studies with Benzene
journal, August 2005

Bhalla, Gaurav; Liu, Xiang Yang; Oxgaard, Jonas
Journal of the American Chemical Society, Vol. 127, Issue 32
https://doi.org/10.1021/ja051532o

CH Activation with an O-Donor Iridium−Methoxo Complex
journal, October 2005

Tenn, William J.; Young, Kenneth J. H.; Bhalla, Gaurav
Journal of the American Chemical Society, Vol. 127, Issue 41
https://doi.org/10.1021/ja051497l

C?H Activation of Alkanes and Arenes Catalyzed by an O-Donor Bis(tropolonato)iridium(III) Complex
journal, February 2005

Bhalla, Gaurav; Periana, Roy A.
Angewandte Chemie International Edition, Vol. 44, Issue 10
https://doi.org/10.1002/anie.200462065

C?H Activation of Alkanes and Arenes Catalyzed by an O-Donor Bis(tropolonato)iridium(III) Complex
journal, February 2005

Bhalla, Gaurav; Periana, Roy A.
Angewandte Chemie, Vol. 117, Issue 10
https://doi.org/10.1002/ange.200462065

Stoichiometric Oxy Functionalization and CH Activation Studies of Cyclometalated Iridium(III) 6-Phenyl-2,2‘-Bipyridine Hydrocarbyl Complexes
journal, April 2007

Young, Kenneth J. H.; Mironov, Oleg A.; Periana, Roy A.
Organometallics, Vol. 26, Issue 9
https://doi.org/10.1021/om0611002

Experimental realization of catalytic CH4 hydroxylation predicted for an iridium NNC pincer complex, demonstrating thermal, protic, and oxidant stability
journal, January 2009

Young, Kenneth J. H.; Oxgaard, Jonas; Ess, Daniel H.
Chemical Communications, Issue 22
https://doi.org/10.1039/b823303a

Intra- and Intermolecular C–H Activation by Bis(phenolate)pyridineiridium(III) Complexes
journal, December 2011

Fu, Ross; Bercaw, John E.; Labinger, Jay A.
Organometallics, Vol. 30, Issue 24
https://doi.org/10.1021/om201069k

C−H Bond Activation by Rhodium(I) Phenoxide and Acetate Complexes: Mechanism of H−D Exchange between Arenes and Water
journal, April 2008

Hanson, Susan Kloek; Heinekey, D. Michael; Goldberg, Karen I.
Organometallics, Vol. 27, Issue 7
https://doi.org/10.1021/om7012259

Controlling the Selectivity for C–H and C–CN Bond Activation at Rhodium: A DFT Examination of Ligand Effects
journal, June 2011

Evans, Meagan E.; Jones, William D.
Organometallics, Vol. 30, Issue 12
https://doi.org/10.1021/om2002602

Oxidative carbonylation of toluene to p-toluic acid catalyzed by rhodium in the presence of vanadium and oxygen
journal, October 2007

Zakzeski, Joseph J.; Bell, Alexis T.
Journal of Molecular Catalysis A: Chemical, Vol. 276, Issue 1-2
https://doi.org/10.1016/j.molcata.2007.06.013

Rhodium(II) Porphyrin Bimetalloradical Complexes: Preparation and Enhanced Reactivity with CH4 and H2
journal, August 1994

Zhang, Xiao-Xiang; Wayland, Bradford B.
Journal of the American Chemical Society, Vol. 116, Issue 17
https://doi.org/10.1021/ja00096a057

Synthesis, characterization, and C–H activation reactions of novel organometallic O-donor ligated Rh(III) complexes
journal, January 2011

Tenn, William J.; Conley, Brian L.; Bischof, Steven M.
Journal of Organometallic Chemistry, Vol. 696, Issue 2
https://doi.org/10.1016/j.jorganchem.2010.09.021

Catalytic Arene H/D Exchange with Novel Rhodium and Iridium Complexes
journal, February 2012

Rhinehart, Jennifer L.; Manbeck, Kimberly A.; Buzak, Sara K.
Organometallics, Vol. 31, Issue 5
https://doi.org/10.1021/om2012419

C−H Activation of Phenyl Imines and 2-Phenylpyridines with [Cp*MCl ₂ ] ₂ (M = Ir, Rh): Regioselectivity, Kinetics, and Mechanism
journal, June 2009

Li, Ling; Brennessel, William W.; Jones, William D.
Organometallics, Vol. 28, Issue 12
https://doi.org/10.1021/om9000742

CH Bond Activation by Rhodium(I) Hydroxide and Phenoxide Complexes
journal, June 2007

Kloek, Susan M.; Heinekey, D. Michael; Goldberg, Karen I.
Angewandte Chemie International Edition, Vol. 46, Issue 25
https://doi.org/10.1002/anie.200700270

CH Bond Activation by Rhodium(I) Hydroxide and Phenoxide Complexes
journal, June 2007

Kloek, Susan M.; Heinekey, D. Michael; Goldberg, Karen I.
Angewandte Chemie, Vol. 119, Issue 25
https://doi.org/10.1002/ange.200700270

Main-Group Compounds Selectively Oxidize Mixtures of Methane, Ethane, and Propane to Alcohol Esters
journal, March 2014

Hashiguchi, B. G.; Konnick, M. M.; Bischof, S. M.
Science, Vol. 343, Issue 6176, p. 1232-1237
https://doi.org/10.1126/science.1249357

Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex
journal, August 2014

Konnick, Michael M.; Hashiguchi, Brian G.; Devarajan, Deepa
Angewandte Chemie International Edition, Vol. 53, Issue 39, p. 10490-10494
https://doi.org/10.1002/anie.201406185

Selective Monooxidation of Light Alkanes Using Chloride and Iodate
journal, May 2014

Fortman, George C.; Boaz, Nicholas C.; Munz, Dominik
Journal of the American Chemical Society, Vol. 136, Issue 23
https://doi.org/10.1021/ja502657g

A homolytic oxy-functionalization mechanism: intermolecular hydrocarbyl migration from M–R to vanadate oxo
journal, January 2014

Cheng, Mu-Jeng; Nielsen, Robert J.; Goddard III, William A.
Chem. Commun., Vol. 50, Issue 75
https://doi.org/10.1039/C4CC03067B

Diplatinum Complexes Supported by Novel Tetradentate Ligands with Quinoline Functionalities for Tandem C−Cl Activation and Dearomatization
journal, December 2008

Tan, Runyu; Jia, Peng; Rao, Yingli
Organometallics, Vol. 27, Issue 24
https://doi.org/10.1021/om800893r

Luminescence and reactivity of 7-azaindole derivatives and complexes
journal, January 2010

Zhao, Shu-Bin; Wang, Suning
Chemical Society Reviews, Vol. 39, Issue 8
https://doi.org/10.1039/c001897j

Low-temperature, palladium(II)-catalyzed, solution-phase oxidation of methane to methanol derivative
journal, January 1991

Kao, Lien Chung; Hutson, Alan C.; Sen, Ayusman
Journal of the American Chemical Society, Vol. 113, Issue 2
https://doi.org/10.1021/ja00002a063

Cobalt-Catalyzed Oxidation of Methane to Methyl Trifluoroacetate by Dioxygen
journal, July 2013

Strassner, Thomas; Ahrens, Sebastian; Muehlhofer, Michael
European Journal of Inorganic Chemistry, Vol. 2013, Issue 21
https://doi.org/10.1002/ejic.201300213

Kinetics and Mechanism of Methane, Methanol, and Dimethyl Ether C−H Activation with Electrophilic Platinum Complexes
journal, February 2006

Owen, Jonathan S.; Labinger, Jay A.; Bercaw, John E.
Journal of the American Chemical Society, Vol. 128, Issue 6
https://doi.org/10.1021/ja056387t

Product Protection, the Key to Developing High Performance Methane Selective Oxidation Catalysts
journal, December 2009

Ahlquist, Mårten; Nielsen, Robert J.; Periana, Roy A.
Journal of the American Chemical Society, Vol. 131, Issue 47
https://doi.org/10.1021/ja903930e

Platinum Catalysts for the High-Yield Oxidation of Methane to a Methanol Derivative
journal, April 1998

Periana, R. A.
Science, Vol. 280, Issue 5363
https://doi.org/10.1126/science.280.5363.560

Accurate First Principles Calculation of Molecular Charge Distributions and Solvation Energies from Ab Initio Quantum Mechanics and Continuum Dielectric Theory
journal, December 1994

Tannor, David J.; Marten, Bryan; Murphy, Robert
Journal of the American Chemical Society, Vol. 116, Issue 26
https://doi.org/10.1021/ja00105a030

New Model for Calculation of Solvation Free Energies: Correction of Self-Consistent Reaction Field Continuum Dielectric Theory for Short-Range Hydrogen-Bonding Effects
journal, January 1996

Marten, Bryan; Kim, Kyungsun; Cortis, Christian
The Journal of Physical Chemistry, Vol. 100, Issue 28
https://doi.org/10.1021/jp953087x

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988

Becke, A. D.
Physical Review A, Vol. 38, Issue 6
https://doi.org/10.1103/PhysRevA.38.3098

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

Becke, Axel D.
The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
https://doi.org/10.1063/1.464913

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988

Lee, Chengteh; Yang, Weitao; Parr, Robert G.
Physical Review B, Vol. 37, Issue 2
https://doi.org/10.1103/PhysRevB.37.785

The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007

Zhao, Yan; Truhlar, Donald G.
Theoretical Chemistry Accounts, Vol. 120, Issue 1-3
https://doi.org/10.1007/s00214-007-0310-x

Density Functionals with Broad Applicability in Chemistry
journal, February 2008

Zhao, Yan; Truhlar, Donald G.
Accounts of Chemical Research, Vol. 41, Issue 2
https://doi.org/10.1021/ar700111a

Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals
journal, January 1985

Hay, P. Jeffrey; Wadt, Willard R.
The Journal of Chemical Physics, Vol. 82, Issue 1, p. 299-310
https://doi.org/10.1063/1.448975

Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
journal, March 1972

Hehre, W. J.; Ditchfield, R.; Pople, J. A.
The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261
https://doi.org/10.1063/1.1677527

Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements
journal, October 1982

Francl, Michelle M.; Pietro, William J.; Hehre, Warren J.
The Journal of Chemical Physics, Vol. 77, Issue 7, p. 3654-3665
https://doi.org/10.1063/1.444267

Correlation consistent valence basis sets for use with the Stuttgart–Dresden–Bonn relativistic effective core potentials: The atoms Ga–Kr and In–Xe
journal, February 2001

Martin, Jan M. L.; Sundermann, Andreas
The Journal of Chemical Physics, Vol. 114, Issue 8
https://doi.org/10.1063/1.1337864

Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, Li-F
journal, October 1983

Clark, Timothy; Chandrasekhar, Jayaraman; Spitznagel, G�nther W.
Journal of Computational Chemistry, Vol. 4, Issue 3
https://doi.org/10.1002/jcc.540040303

Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980

Krishnan, R.; Binkley, J. S.; Seeger, R.
The Journal of Chemical Physics, Vol. 72, Issue 1
https://doi.org/10.1063/1.438955

A fast intrinsic localization procedure applicable for a b i n i t i o and semiempirical linear combination of atomic orbital wave functions
journal, May 1989

Pipek, János; Mezey, Paul G.
The Journal of Chemical Physics, Vol. 90, Issue 9
https://doi.org/10.1063/1.456588

Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton
journal, August 2006

Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.
The Journal of Physical Chemistry B, Vol. 110, Issue 32
https://doi.org/10.1021/jp063552y

The Proton's Absolute Aqueous Enthalpy and Gibbs Free Energy of Solvation from Cluster-Ion Solvation Data
journal, October 1998

Tissandier, Michael D.; Cowen, Kenneth A.; Feng, Wan Yong
The Journal of Physical Chemistry A, Vol. 102, Issue 40
https://doi.org/10.1021/jp982638r

Relationship between the gas-phase entropies of molecules and their entropies of solvation in water and 1-octanol
journal, July 1980

Wertz, David H.
Journal of the American Chemical Society, Vol. 102, Issue 16
https://doi.org/10.1021/ja00536a033

Valence bond description of antiferromagnetic coupling in transition metal dimers
journal, May 1981

Noodleman, Louis
The Journal of Chemical Physics, Vol. 74, Issue 10
https://doi.org/10.1063/1.440939

Broken symmetry effects in the He(I) valence photoelectron spectrum of Se(CN) ₂
journal, June 1982

Jonkers, G.; de Lange, C. A.; Noodleman, L.
Molecular Physics, Vol. 46, Issue 3
https://doi.org/10.1080/00268978200101431

Models for ferredoxins: electronic structures of iron-sulfur clusters with one, two, and four iron atoms
journal, June 1985

Noodleman, Louis; Norman, Joe G.; Osborne, Joseph H.
Journal of the American Chemical Society, Vol. 107, Issue 12
https://doi.org/10.1021/ja00298a004

Ligand spin polarization and antiferromagnetic coupling in transition metal dimers
journal, November 1986

Noodleman, Louis; Davidson, Ernest R.
Chemical Physics, Vol. 109, Issue 1
https://doi.org/10.1016/0301-0104(86)80192-6

Symmetry breaking and ionization from symmetry equivalent inner shells and lone pairs in Xα theory
journal, January 1982

Noodleman, L.; Post, D.; Baerends, E. J.
Chemical Physics, Vol. 64, Issue 1
https://doi.org/10.1016/0301-0104(82)85012-X

A model for the spin states of high-potential iron-sulfur [Fe4S4]3+ proteins
journal, October 1988

Noodleman, Louis
Inorganic Chemistry, Vol. 27, Issue 20
https://doi.org/10.1021/ic00293a051

Broken symmetry analysis of spin coupling in iron-sulfur clusters
journal, February 1988

Noodleman, Louis.; Case, David A.; Aizman, Arie.
Journal of the American Chemical Society, Vol. 110, Issue 4
https://doi.org/10.1021/ja00212a003

Simple spin correction of unrestricted density-functional calculation
journal, June 1996

Ovchinnikov, Alexander A.; Labanowski, Jan K.
Physical Review A, Vol. 53, Issue 6
https://doi.org/10.1103/PhysRevA.53.3946

Potential energy curves of fluorine, nitrogen and ethylene calculated by approximately projected unrestricted Hartree-Fock and Møller-Plesset perturbation methods
journal, May 1989

Takahara, Y.; Yamaguchi, K.; Fueno, T.
Chemical Physics Letters, Vol. 157, Issue 3
https://doi.org/10.1016/0009-2614(89)87236-7

Approximately spin-projected geometry optimization method and its application to di-chromium systems
journal, July 2007

Kitagawa, Yasutaka; Saito, Toru; Ito, Masahide
Chemical Physics Letters, Vol. 442, Issue 4-6
https://doi.org/10.1016/j.cplett.2007.05.082

Approximate spin-projected broken symmetry energies from optimized orbitals that are unrestricted in active pairs
journal, October 2011

Mak, Adrian M.; Lawler, Keith V.; Head-Gordon, Martin
Chemical Physics Letters, Vol. 515, Issue 1-3
https://doi.org/10.1016/j.cplett.2011.08.076

Prediction of molecular properties and molecular spectroscopy with density functional theory: From fundamental theory to exchange-coupling
journal, March 2009

Neese, Frank
Coordination Chemistry Reviews, Vol. 253, Issue 5-6
https://doi.org/10.1016/j.ccr.2008.05.014

Works referencing / citing this record:

The Direct Catalytic Oxidation of Methane to Methanol-A Critical Assessment
journal, November 2017

Ravi, Manoj; Ranocchiari, Marco; van Bokhoven, Jeroen A.
Angewandte Chemie International Edition, Vol. 56, Issue 52
https://doi.org/10.1002/anie.201702550

Similar records in OSTI.GOV collections:

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

Journal Article Fu, Ross; O'Reilly, Matthew; Nielsen, Robert; ... - Chemistry - A European Journal
https://doi.org/10.1002/chem.201405460
Rhodium Bis(quinolinyl)benzene Complexes for Methane Activation and Functionalization

Journal Article Fu, Ross; O'Reilly, Matthew; Nielsen, Robert; ... - Chemistry - A European Journal

A series of rhodium (III) bis(quinolinyl)benzene (bisq^x) 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 (bisq^x) ligand candidates involving different functional groups to determine the impact on RhIII(bisq^x) 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 Rh^III coordinated to unsubstituted bis(quinolinyl)benzene (bisq). Support is also found for the prediction that the η²-benzene coordinationmore »« less
Cited by 22
https://doi.org/10.1002/chem.201405460

Full Text Available
Reductive Functionalization of a Rhodium(III)–Methyl Bond in Acidic Media: Key Step in the Electrophilic Functionalization of Methane

Journal Article O’Reilly, Matthew; Pahls, Dale; Cundari, Thomas; ... - Organometallics

The reductive functionalization of RhIII–Me bonds in acids is a key step for RhI/III-based catalysts for methane functionalization. Heating electronic-rich [tBu3terpy]Rh(Me)(Cl)I (1; tBu3terpy = 4,4',4''-tri-tert-butylterpyridine) in H2O, AcOD, or trifluoroacetic acid (HTFA) released a stoichiometric amount of methane. With use of a less donating ligand, [(NO2)3terpy]Rh(Me)(Cl)I (2; (NO2)3terpy = 4,4',4''-trinitroterpyridine), a mixture of CH4 and CH3X (X = Cl, TFA, OAc, OH) was obtained. The selectivity between MeX and CH4 was found to be dependent on the halide present (I– or Cl–). In a key experiment with the removal of one halide from 2, {[(NO2)3terpy]Rh(Me)Cl}{BF4} (3) was completely protonated inmore »« less
https://doi.org/10.1021/om5008456
Rhodium complexes bearing tetradentate diamine-bis(phenolate) ligands

Journal Article Liu, Xiang; Lokare, Kapil; Ganesh, Somesh; ... - Dalton Transactions
https://doi.org/10.1039/C0DT00997K
DFT Virtual Screening Identifies Rhodium-Amidinate Complexes as Potential Homogeneous Catalysts for Methane-to-Methanol Oxidation

Journal Article Fu, Ross; Nielsen, Robert; Goddard, III, William - ACS Catal.
https://doi.org/10.1021/cs5005322

Similar Records

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

Citation Formats

Understanding and exploiting C–H bond activation journal, May 2002

Alkane C–H activation and functionalization with homogeneous transition metal catalysts: a century of progress—a new millennium in prospect journal, January 2001

Methane activation in homogeneous systems journal, April 1995

Selective alkane oxidation: hot and cold approaches to a hot problem journal, September 2004

A Mercury-Catalyzed, High-Yield System for the Oxidation of Methane to Methanol journal, January 1993

New Catalyst Systems for the Catalytic Conversion of Methane into Methanol journal, May 2002

Neue Katalysatorsysteme für die katalytische Oxidation von Methan zu Methanol journal, May 2002

Activation of Methane and Ethane and Their Selective Oxidation to the Alcohols in Protic Media journal, February 1994

Selective Intermolecular Carbon-Hydrogen Bond Activation by Synthetic Metal Complexes in Homogeneous Solution journal, March 1995

Alkane C−H Activation and Catalysis by an O-Donor Ligated Iridium Complex journal, November 2003

Mechanism of Homogeneous Ir(III) Catalyzed Regioselective Arylation of Olefins journal, January 2004

Synthesis, Structure, and Reactivity of O-Donor Ir(III) Complexes: C−H Activation Studies with Benzene journal, August 2005

CH Activation with an O-Donor Iridium−Methoxo Complex journal, October 2005

C?H Activation of Alkanes and Arenes Catalyzed by an O-Donor Bis(tropolonato)iridium(III) Complex journal, February 2005

C?H Activation of Alkanes and Arenes Catalyzed by an O-Donor Bis(tropolonato)iridium(III) Complex journal, February 2005

Stoichiometric Oxy Functionalization and CH Activation Studies of Cyclometalated Iridium(III) 6-Phenyl-2,2‘-Bipyridine Hydrocarbyl Complexes journal, April 2007

Experimental realization of catalytic CH4 hydroxylation predicted for an iridium NNC pincer complex, demonstrating thermal, protic, and oxidant stability journal, January 2009

Intra- and Intermolecular C–H Activation by Bis(phenolate)pyridineiridium(III) Complexes journal, December 2011

C−H Bond Activation by Rhodium(I) Phenoxide and Acetate Complexes: Mechanism of H−D Exchange between Arenes and Water journal, April 2008

Controlling the Selectivity for C–H and C–CN Bond Activation at Rhodium: A DFT Examination of Ligand Effects journal, June 2011

Oxidative carbonylation of toluene to p-toluic acid catalyzed by rhodium in the presence of vanadium and oxygen journal, October 2007

Rhodium(II) Porphyrin Bimetalloradical Complexes: Preparation and Enhanced Reactivity with CH4 and H2 journal, August 1994

Synthesis, characterization, and C–H activation reactions of novel organometallic O-donor ligated Rh(III) complexes journal, January 2011

Catalytic Arene H/D Exchange with Novel Rhodium and Iridium Complexes journal, February 2012

C−H Activation of Phenyl Imines and 2-Phenylpyridines with [Cp*MCl 2 ] 2 (M = Ir, Rh): Regioselectivity, Kinetics, and Mechanism journal, June 2009

CH Bond Activation by Rhodium(I) Hydroxide and Phenoxide Complexes journal, June 2007

CH Bond Activation by Rhodium(I) Hydroxide and Phenoxide Complexes journal, June 2007

Main-Group Compounds Selectively Oxidize Mixtures of Methane, Ethane, and Propane to Alcohol Esters journal, March 2014

Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex journal, August 2014

Selective Monooxidation of Light Alkanes Using Chloride and Iodate journal, May 2014

A homolytic oxy-functionalization mechanism: intermolecular hydrocarbyl migration from M–R to vanadate oxo journal, January 2014

Diplatinum Complexes Supported by Novel Tetradentate Ligands with Quinoline Functionalities for Tandem C−Cl Activation and Dearomatization journal, December 2008

Luminescence and reactivity of 7-azaindole derivatives and complexes journal, January 2010

Low-temperature, palladium(II)-catalyzed, solution-phase oxidation of methane to methanol derivative journal, January 1991

Cobalt-Catalyzed Oxidation of Methane to Methyl Trifluoroacetate by Dioxygen journal, July 2013

Kinetics and Mechanism of Methane, Methanol, and Dimethyl Ether C−H Activation with Electrophilic Platinum Complexes journal, February 2006

Product Protection, the Key to Developing High Performance Methane Selective Oxidation Catalysts journal, December 2009

Platinum Catalysts for the High-Yield Oxidation of Methane to a Methanol Derivative journal, April 1998

Accurate First Principles Calculation of Molecular Charge Distributions and Solvation Energies from Ab Initio Quantum Mechanics and Continuum Dielectric Theory journal, December 1994

New Model for Calculation of Solvation Free Energies: Correction of Self-Consistent Reaction Field Continuum Dielectric Theory for Short-Range Hydrogen-Bonding Effects journal, January 1996

Density-functional exchange-energy approximation with correct asymptotic behavior journal, September 1988

Density‐functional thermochemistry. III. The role of exact exchange journal, April 1993

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal, January 1988

The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals journal, July 2007

Density Functionals with Broad Applicability in Chemistry journal, February 2008

Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals journal, January 1985

Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules journal, March 1972

Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements journal, October 1982

Correlation consistent valence basis sets for use with the Stuttgart–Dresden–Bonn relativistic effective core potentials: The atoms Ga–Kr and In–Xe journal, February 2001

Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, Li-F journal, October 1983

Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions journal, January 1980

A fast intrinsic localization procedure applicable for a b i n i t i o and semiempirical linear combination of atomic orbital wave functions journal, May 1989

Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton journal, August 2006

The Proton's Absolute Aqueous Enthalpy and Gibbs Free Energy of Solvation from Cluster-Ion Solvation Data journal, October 1998

Relationship between the gas-phase entropies of molecules and their entropies of solvation in water and 1-octanol journal, July 1980

Valence bond description of antiferromagnetic coupling in transition metal dimers journal, May 1981

Broken symmetry effects in the He(I) valence photoelectron spectrum of Se(CN) 2 journal, June 1982

Models for ferredoxins: electronic structures of iron-sulfur clusters with one, two, and four iron atoms journal, June 1985

Ligand spin polarization and antiferromagnetic coupling in transition metal dimers journal, November 1986

Symmetry breaking and ionization from symmetry equivalent inner shells and lone pairs in Xα theory journal, January 1982

A model for the spin states of high-potential iron-sulfur [Fe4S4]3+ proteins journal, October 1988

Broken symmetry analysis of spin coupling in iron-sulfur clusters journal, February 1988

Simple spin correction of unrestricted density-functional calculation journal, June 1996

Potential energy curves of fluorine, nitrogen and ethylene calculated by approximately projected unrestricted Hartree-Fock and Møller-Plesset perturbation methods journal, May 1989

Approximately spin-projected geometry optimization method and its application to di-chromium systems journal, July 2007

Approximate spin-projected broken symmetry energies from optimized orbitals that are unrestricted in active pairs journal, October 2011

Prediction of molecular properties and molecular spectroscopy with density functional theory: From fundamental theory to exchange-coupling journal, March 2009

The Direct Catalytic Oxidation of Methane to Methanol-A Critical Assessment journal, November 2017

Understanding and exploiting C–H bond activation
journal, May 2002

Alkane C–H activation and functionalization with homogeneous transition metal catalysts: a century of progress—a new millennium in prospect
journal, January 2001

Methane activation in homogeneous systems
journal, April 1995

Selective alkane oxidation: hot and cold approaches to a hot problem
journal, September 2004

A Mercury-Catalyzed, High-Yield System for the Oxidation of Methane to Methanol
journal, January 1993

New Catalyst Systems for the Catalytic Conversion of Methane into Methanol
journal, May 2002

Neue Katalysatorsysteme für die katalytische Oxidation von Methan zu Methanol
journal, May 2002

Activation of Methane and Ethane and Their Selective Oxidation to the Alcohols in Protic Media
journal, February 1994

Selective Intermolecular Carbon-Hydrogen Bond Activation by Synthetic Metal Complexes in Homogeneous Solution
journal, March 1995

Alkane C−H Activation and Catalysis by an O-Donor Ligated Iridium Complex
journal, November 2003

Mechanism of Homogeneous Ir(III) Catalyzed Regioselective Arylation of Olefins
journal, January 2004

Synthesis, Structure, and Reactivity of O-Donor Ir(III) Complexes: C−H Activation Studies with Benzene
journal, August 2005

CH Activation with an O-Donor Iridium−Methoxo Complex
journal, October 2005

C?H Activation of Alkanes and Arenes Catalyzed by an O-Donor Bis(tropolonato)iridium(III) Complex
journal, February 2005

C?H Activation of Alkanes and Arenes Catalyzed by an O-Donor Bis(tropolonato)iridium(III) Complex
journal, February 2005

Stoichiometric Oxy Functionalization and CH Activation Studies of Cyclometalated Iridium(III) 6-Phenyl-2,2‘-Bipyridine Hydrocarbyl Complexes
journal, April 2007

Experimental realization of catalytic CH4 hydroxylation predicted for an iridium NNC pincer complex, demonstrating thermal, protic, and oxidant stability
journal, January 2009

Intra- and Intermolecular C–H Activation by Bis(phenolate)pyridineiridium(III) Complexes
journal, December 2011

C−H Bond Activation by Rhodium(I) Phenoxide and Acetate Complexes: Mechanism of H−D Exchange between Arenes and Water
journal, April 2008

Controlling the Selectivity for C–H and C–CN Bond Activation at Rhodium: A DFT Examination of Ligand Effects
journal, June 2011

Oxidative carbonylation of toluene to p-toluic acid catalyzed by rhodium in the presence of vanadium and oxygen
journal, October 2007

Rhodium(II) Porphyrin Bimetalloradical Complexes: Preparation and Enhanced Reactivity with CH4 and H2
journal, August 1994

Synthesis, characterization, and C–H activation reactions of novel organometallic O-donor ligated Rh(III) complexes
journal, January 2011

Catalytic Arene H/D Exchange with Novel Rhodium and Iridium Complexes
journal, February 2012

C−H Activation of Phenyl Imines and 2-Phenylpyridines with [Cp*MCl ₂ ] ₂ (M = Ir, Rh): Regioselectivity, Kinetics, and Mechanism
journal, June 2009

CH Bond Activation by Rhodium(I) Hydroxide and Phenoxide Complexes
journal, June 2007

CH Bond Activation by Rhodium(I) Hydroxide and Phenoxide Complexes
journal, June 2007

Main-Group Compounds Selectively Oxidize Mixtures of Methane, Ethane, and Propane to Alcohol Esters
journal, March 2014

Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex
journal, August 2014

Selective Monooxidation of Light Alkanes Using Chloride and Iodate
journal, May 2014

A homolytic oxy-functionalization mechanism: intermolecular hydrocarbyl migration from M–R to vanadate oxo
journal, January 2014

Diplatinum Complexes Supported by Novel Tetradentate Ligands with Quinoline Functionalities for Tandem C−Cl Activation and Dearomatization
journal, December 2008

Luminescence and reactivity of 7-azaindole derivatives and complexes
journal, January 2010

Low-temperature, palladium(II)-catalyzed, solution-phase oxidation of methane to methanol derivative
journal, January 1991

Cobalt-Catalyzed Oxidation of Methane to Methyl Trifluoroacetate by Dioxygen
journal, July 2013

Kinetics and Mechanism of Methane, Methanol, and Dimethyl Ether C−H Activation with Electrophilic Platinum Complexes
journal, February 2006

Product Protection, the Key to Developing High Performance Methane Selective Oxidation Catalysts
journal, December 2009

Platinum Catalysts for the High-Yield Oxidation of Methane to a Methanol Derivative
journal, April 1998

Accurate First Principles Calculation of Molecular Charge Distributions and Solvation Energies from Ab Initio Quantum Mechanics and Continuum Dielectric Theory
journal, December 1994

New Model for Calculation of Solvation Free Energies: Correction of Self-Consistent Reaction Field Continuum Dielectric Theory for Short-Range Hydrogen-Bonding Effects
journal, January 1996

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988

The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007

Density Functionals with Broad Applicability in Chemistry
journal, February 2008

Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals
journal, January 1985

Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
journal, March 1972

Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements
journal, October 1982

Correlation consistent valence basis sets for use with the Stuttgart–Dresden–Bonn relativistic effective core potentials: The atoms Ga–Kr and In–Xe
journal, February 2001

Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, Li-F
journal, October 1983

Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980

A fast intrinsic localization procedure applicable for a b i n i t i o and semiempirical linear combination of atomic orbital wave functions
journal, May 1989

Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton
journal, August 2006

The Proton's Absolute Aqueous Enthalpy and Gibbs Free Energy of Solvation from Cluster-Ion Solvation Data
journal, October 1998

Relationship between the gas-phase entropies of molecules and their entropies of solvation in water and 1-octanol
journal, July 1980

Valence bond description of antiferromagnetic coupling in transition metal dimers
journal, May 1981

Broken symmetry effects in the He(I) valence photoelectron spectrum of Se(CN) ₂
journal, June 1982

Models for ferredoxins: electronic structures of iron-sulfur clusters with one, two, and four iron atoms
journal, June 1985

Ligand spin polarization and antiferromagnetic coupling in transition metal dimers
journal, November 1986

Symmetry breaking and ionization from symmetry equivalent inner shells and lone pairs in Xα theory
journal, January 1982

A model for the spin states of high-potential iron-sulfur [Fe4S4]3+ proteins
journal, October 1988

Broken symmetry analysis of spin coupling in iron-sulfur clusters
journal, February 1988

Simple spin correction of unrestricted density-functional calculation
journal, June 1996

Potential energy curves of fluorine, nitrogen and ethylene calculated by approximately projected unrestricted Hartree-Fock and Møller-Plesset perturbation methods
journal, May 1989

Approximately spin-projected geometry optimization method and its application to di-chromium systems
journal, July 2007

Approximate spin-projected broken symmetry energies from optimized orbitals that are unrestricted in active pairs
journal, October 2011

Prediction of molecular properties and molecular spectroscopy with density functional theory: From fundamental theory to exchange-coupling
journal, March 2009

The Direct Catalytic Oxidation of Methane to Methanol-A Critical Assessment
journal, November 2017