Electrophilic Oxidation Catalysis

Project Details

The ability to use alkanes directly as a feedstock for the chemical production of alcohols and other organics would significantly impact the chemical industry. The development of such technologies would take advantage of the tremendous reserves of natural gas within the U.S.

Using the large knowledge base gained from previous detailed mechanistic studies on the well-defined platinum-based Shilov systems, we are investigating electrophilic catalysts of other metals. Efforts are focused on developing and applying fundamental mechanistic understanding of C-H bond activation to the development of new catalytic systems for alkane and arene oxidation. CENTC is exploring new strategies for activating C-H bonds, for functionalizing metal-alkyl and metal-aryl bonds, and for creating C-C and C-O bonds. During this process, fundamentally new catalysts have been conceived, tested, and employed. The development of a catalytic system that can perform the partial oxidation of alkanes using O₂as an oxidant is a specific goal.

Senior Investigators 

Examples of Electrophilic Oxidation Catalysts Being Investigated

Recent Publications and Patents

  • Cook, A. K.; Sanford, M. S. "Mechanism of the Palladium-Catalyzed Arene C-H Acetoxylation: A Comparison of Catalysts and Ligand Effects", J. Am. Chem. Soc., 2015, 137, 3109-3118.
    (DOI: 10.1021/jacs.5b00238)
  • Lehman, M. C.; Pahls, D. R.; Meredith, J. M.; Sommer, R. D.; Heinekey, D. M.; Cundari, T. R.; Ison, E. A. "Oxyfunctionalization with Cp*IrIII(NHC)(Me)(Cl) with O2: Identification of a Rare Bimetallic IrIV µ-Oxo Intermediate", J. Am. Chem. Soc., 2015, 137, 3574-3584.
    (DOI: 10.1021/ja512905t)
  • Frasco, D. A.; Sommer, R. D.; Ison, E. A. "ortho-C–H Activation of Thiobenzoic Acid: Synthesis, Characterization, and Reactivity of Iridium Thiobenzoate Complexes", Organometallics, 2015, 34, 275-279.
    (DOI: 10.1021/om501115u)
  • Pahls, D. R.; Allen, K. E.; Goldberg, K. I.; Cundari, T. R. "Understanding the Effect of Ancillary Ligands on Concerted Metalation–Deprotonation by (dmPhebox)Ir(OAc)2(H2O) Complexes: A DFT Study", Organometallics, 2014, 33, 6413-6419. (DOI: 10.1021/om500752m)
  • Allen, K. E.; Heinekey, D. M; Goldman, A. S.; Goldberg, K. I. "Regeneration of an Ir(III) Complex Active for Alkane Dehydrogenation Using Molecular Oxygen", Organometallics, 2014, 33, 1337-1340.  (DOI: 10.1021/om401241e) 
  • Dobereiner, G. E.; Yuan, J.; Schrock, R. R.; Goldman, A. S.; Hackenberg, J. D. "Catalytic Synthesis of n-Alkyl Arenes through Alkyl Group Cross Metathesis", J. Am. Chem. Soc., 2013, 135, 12572-12575. (DOI: 10.1021/ja4066392)
  • Cook, A. K.; Emmert, M. H.; Sanford, M. S. "Steric Control of Site Selectivity in the Pd-Catalyzed C–H Acetoxylation of Simple Arenes", Org. Lett., 2013, 15, 5428-5431. (DOI: 10.1021/ol4024248)
  • Gary, J. B.; Cook, A. K.; Sanford, M. S. "Palladium Catalysts Containing Pyridinium-Substituted Pyridine Ligands for the C–H Oxygenation of Benzene with K2S2O8", ACS Catal., 2013, 3, 700-703. (DOI: 10.1021/cs300786j)
  • Manbeck, K. A.; Brennessel, W. W.; Jones, W. D. "Examination of a Dicationic Rhodium Methyl Aquo Complex", Inorg. Chim. Acta, 2013, 397, 140-143. (DOI: 10.1016/j.ica.2012.12.002)
  • Frasco, D. A.; Lilly, C. P.; Boyle, P. D.; Ison, E. A. "Cp*Ir(III)-Catalyzed Oxidative Coupling of Benzoic Acis with Alkynes", ACS Catal., 2013, 3, 2421-2429. (DOI: 10.1021/cs400656q)
  • Lehman, M. C.; Gary, J. B.; Boyle, P. D.; Sanford, M. S.; Ison, E. A. "Effect of Solvent and Ancillary Ligands on the Catalytic H/D Exchange Reactivity of Cp*Ir(L) Complexes", ACS Catal., 2013, 3, 2304-2310. (DOI: 10.1021/cs400420n)
  • Allen, K. E.; Heinekey, D. M.; Goldman, A. S.; Goldberg, K. I. "Alkane Dehydrogenation by C-H Activation at Iridium(III)", Organometallics, 2013, 32, 1579-1582. (DOI: 10.1021/om301267c)

    • BACK to RESEARCH THEMES

© 2007 - 2024 Center for Enabling New Technologies Through Catalysis
centcweb@u.washington.edu

This work was supported by NSF under the CCI Center for Enabling New Technologies Through Catalysis, CHE-1205189. Any opinions, findings, and conclusions or recommendations expressed here are those of the authors and do not necessarily reflect the views of the National Science Foundation (NSF).

CENTC logo