Formally Copper(III) Complexes Relevant to Oxidizing Intermediates in Enzymes

William B. Tolman
University of Minnesota
Nov. 30 13:30~14:15


Characterization of copper intermediates in enzymes and other catalysts that attack strong C-H bonds is important for unraveling oxidation catalysis mechanisms and, ultimately, designing new, more efficient catalytic systems. New insights into the nature of such intermediates may be obtained through the design, synthesis, and characterization of copper-oxygen complexes. Particular impetus for such studies comes from provocative proposals of novel structures for the oxidizing species in particulate methane monooxygenase (pMMO) and a variety of monocopper enzymes, of which lytic polysaccharide monooxygenase (LPMO) is of particular note due to its novel structure and its utility in biotechnology. In work aimed at synthesizing molecules with such cores, we have turned to the use of strongly electron donating carboxamide ligands designed to stabilize copper in high oxidation states, and have studied a number of intriguing species featuring Cu(III) centers. Recent progress toward the characterization of the structures and properties of such species will be described, and new ideas about how enzymes like pMMO and LPMO might operate will be presented.


General References

  1. Copper-Oxygen Complexes Revisited: Structures, Spectroscopy, and Reactivity. Courtney E. Elwell, Nicole L. Gagnon, Benjamin D. Neisen, Debanjan Dhar, Andrew D. Spaeth, Gereon M. Yee, and William B. Tolman*, Chem. Rev. 2017, 117, 2059–2107. DOI: 10.1021/acs.chemrev.6b00636.
  2. [CuO]+ and [CuOH]2+ Complexes: Intermediates in Oxidation Catalysis?. Nicole Gagnon and William B. Tolman, Acc. Chem. Res., 2015, 48, 2126–2131. (DOI: 10.1021/acs.accounts.5b00169)
  3. Perturbing the Copper(III)-Hydroxide Unit Through Ligand Structural Variation. Debanjan Dhar, Gereon M. Yee, Andrew D. Spaeth, David W. Boyce, Hongtu Zhang, Büsra Dereli, Christopher J. Cramer,* and William B. Tolman,* J. Am. Chem. Soc. 2016, 138, 356–368 (DOI: 10.1021/jacs.5b10985).
  4. Reactivity of the Copper(III)-Hydroxide Unit with Phenols. Debanjan Dhar, Gereon M. Yee, Todd F. Markle, James M. Mayer*, and William B. Tolman*, Chemical Science, 2017, 8, 1075 – 1085. DOI: 10.1039/c6sc03039d.
  5. Determination of the Cu(III)-OH Bond Distance by Resonance Raman Spectroscopy using a Normalized Version of Badger’s Rule. Andrew D. Spaeth, Nicole L. Gagnon, Debanjan Dhar, Gereon M. Yee, and William B. Tolman*, J. Am. Chem. Soc. 2017, 139, 4477–4485. DOI: 10.1021/jacs.7b00210.
  6. Formally Copper(III)-alkylperoxo complexes as models of possible intermediates in monooxygenase enzymes. Benjamin D. Neisen, Nicole L. Gagnon, Debanjan Dhar, Andrew D. Spaeth, and William B. Tolman*, J. Am. Chem. Soc. 2017, 139, 10220-10223. DOI: 10.1021/jacs.7b05754.


Professional Career

  • 1990-Present, Assistant, Associate, and Full Professor, University of Minnesota
  • 1987-1990, Postdoctoral Fellow, Massachusetts Insitute of Technology


Academic Activity

  • 2013-Present, Editor-in-Chief; Inorganic Chemistry (ACS)
  • 2009-2017, Chair, Department of Chemistry, University of Minnesota
  • 2015-Present, Chair, ACS Publications Peer Review Advisory Group (ACS)
  • 2015-Present, Member External Advisory Board; Chemical & Engineering News (ACS)
  • 2011-2016, Member, Advisory Board; Petroleum Research Fund (ACS)


Awards and Honors

  • 2017, ACS Award for Distinguished Service in the Advancement of Inorganic Chemistry
  • 2016, Frontiers Award, Max Planck Institute for Chemical Energy Conversion
  • 2012, Charles E. Bowers Teaching Award, College of Science & Engineering, University of Minnesota
  • 2010, Fellow of the American Chemical Society
  • 2006, Fellow of the American Association for the Advancement of Science
  • 2005, Lee Irvin Smith Professorship (University of Minnesota)
  • 2004, Alexander von Humboldt Foundation Research Award (@Technical University of Munich)
  • 2001, Buck-Whitney Medal (ACS Eastern New York Section)
  • 2000, Distinguished McKnight University Professorship (University of Minnesota)
  • 1998, George W. Taylor Award for Excellence in Research (University of Minnesota)
  • 1994, Camille & Henry Dreyfus Teacher-Scholar Award
  • 1993, National Young Investigator Award (National Science Foundation)