Senior 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. Mich.).

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.

Published Papers:

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”, Organometallics, 2012, ASAP.
(DOI: 10.1021/om2012166)

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”, Organometallics, 2012, ASAP.
(DOI: 10.1021/om2012419)

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, 50, 9409-9412.
(DOI: 10.1021/om200343b)

Engelman, K. L.; Feng, Y.; Ison, E. A. “C-H Bond Functionalization of Benzoic Acid: Catalytic Synthesis of 2-Hydroxy-6H-benzo[c]chromen-6-ones using (Cp*IrCl2)2”, pan style="font-style: italic;">Organometallics, 2011, 30, 4572-4577.
(DOI: 10.1021/om200343b)

Schultz, K. M.; Goldberg, K. I.; Gusev, D. G.; Heinekey, D. M. “Synthesis, Structure and Reactivity of Iridium NHC Pincer Complexes”, Organometallics, 2011, 30, 1429-1437.
(DOI: 10.1021/om101024x)

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, 49, 5884-5886.
(DOI: 10.1002/anie.201002351)

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, 29, 2857.
(DOI: 10.1021/om100018x)

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.
(DOI: 10.1021/om900889k)

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.
(DOI: 10.1021/om900495n)

Wesley H. Bernskoetter, Cynthia K. Schauer, Karen I. Goldberg, and Maurice Brookhart, "Characterization of a Rhodium(I) σ-Methane Complex in Solution", Science, 2009, 326, 553-556.
(10.1126/science.1177485)

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, 28, 3546-3551.
(DOI: 10.1021/ja901706b)

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.
(DOI: 10.1021/om900186j)

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)