Center for Enabling New Technologies Through Catalysis
A NSF Center for Chemical Innovation
A New Generation of Electrophilic Oxidation Catalysts
Investigators: Prof. Tom
Cundari (U. North Texas), Prof. Karen Goldberg (U.
Wash.), Prof. Mike Heinekey (U. Wash.), Prof. Elon
Ison (North Carolina State U.), Prof. William
Jones (U. Rochester), Prof. Melanie Sanford (U.
The ability to use alkanes directly as a feedstock for the chemical production of alcohols and other organics would significantly impact the chemical industry. Some thirty years after Shilov’s initial discovery of platinum-catalyzed alkane oxidation, platinum-based systems continue to represent some of the most promising leads for the direct conversion of alkanes to alcohols on industrially viable scales. Other late transition metals such as iridium and rhodium are also known to activate alkanes via a two-electron couple and could in principle perform similar Shilov-type chemisty, perhaps even more successfully than platinum. Surprisingly, other metals have not been extensively explored for this purpose. Using the large knowledge base gained from detailed mechanistic studies on the well-defined platinum systems, related electrophilic catalysts of other metals are under investigation. Efforts are focused on developing and applying fundamental mechanistic understanding of C-H bond activation to the development of new catalytic systems for alkane oxidation.
Natural gas reserves rival those of petroleum. Therefore, methane, the main component of natural gas, has the potential of serving as a valuable feedstock and of being a complementary source of energy to petroleum well into the 21st century. To this end, the discovery of direct and thus more economical methods for methane oxidation technology represents the greatest potential in this field.
Meredith, J. M.; Robinson, R. Jr.; Goldberg, K. I.;
Kaminsky, W.; Heinekey, D. M. “C–H Bond Activation by Cationic Iridium(III) NHC
Complexes: A Combined Experimental and Computational Study”,
Rhinehart, J. L.; Manbeck, K. A.; Buzak, S. K.; Lippa, G. M.; Brennessel, W. W.; Goldberg, K. I.; Jones, W. D.
“Catalytic Arene H/D Exchange with Novel Rhodium and Iridium Complexes”,
Emmert, M. H.; Cook, A.
K.; Xie, Y. J.; Sanford, M. S. “Remarkably
High Reactivity of Pd(OAc)2/Pyridine
Catalysts: Nondirected C-H Oxygenation of
Arenes”, Angew. Chem. Int. Ed., 2011,
Engelman, K. L.; Feng,
Y.; Ison, E. A. “C-H Bond
Functionalization of Benzoic Acid:
Catalytic Synthesis of
(Cp*IrCl2)2”, pan style="font-style:
Schultz, K. M.; Goldberg,
K. I.; Gusev, D. G.; Heinekey, D. M.
“Synthesis, Structure and Reactivity of
Iridium NHC Pincer Complexes”, Organometallics,
Emmert, M. H.; Gary, J.
B.; Villalobos, J. M.; Sanford, M. S.,
"Platinum and Palladium Complexes
Containing Cationic Ligands as Catalysts
for Arene H/D Exchange and Oxidation",
Angew. Chem. Int. Ed. Eng., 2010,
Feng, Y.; Jiang, B.;
Boyle, P. A.; Ison, E. A., "Effect of
Ancillary Ligands and Solvents on H/D
Exchange Reactions Catalyzed by Cp*Ir
Complexes", Organometallics, 2010,
Villalobos, J. M.;
Hickman, A. J.; Sanford, M. S.,
"Platinum(II) Complexes Containing
Quaternized Nitrogen Ligands: Synthesis,
Stability, and Evaluation as Catalysts for
Methane and Benzene H/D Exchange", Organometallics,
2010, 29, 257-262.
Hickman, A.; Villalobos,
J. A.; Sanford, M. S., "A Quantitative
Method to Assay Platinum Catalysts for
Benzene H/D Exchange", Organometallics,
2009, 28, 5316-5322.
Wesley H. Bernskoetter,
Cynthia K. Schauer, Karen I. Goldberg, and
Maurice Brookhart, "Characterization of a
Rhodium(I) σ-Methane Complex in Solution",
Bernskoetter, W. H.;
Hanson, S. K.; Buzak, S. K.; Davis, Z.;
White, P. S.; Swartz, R.; Goldberg, K. I.;
Brookhart, M. “Investigations of Iridium
Mediated Reversible C-H Bond Cleavage:
Characterization of a 16-Electron
Iridium(III) Methyl Hydride Complex”, J.
Am. Chem. Soc., 2009,
Meredith, J. M.;
Goldberg, K. I.; Kaminsky, W.; Heinekey,
D. M. “Dinuclear Iridium Complexes
Containing Cp* and Carbonyl Ligands:
Synthesis, Structure and Reactivity” Organometallics,
2009, 28, 3546-3551.
Hanson, S. K.; Heinekey, D. M.; Goldberg, K. I. "C-H Bond Activation by Rhodium(I) Phenoxide and Acetate Complexes: Mechanism of H−D Exchange between Arenes and Water" Organometallics, 2008, 27(7), 1454-1463. (DOI: 10.1021/om7012259)
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Through Catalysis is a National Science Foundation
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