Faculty Yale

James M. Mayer

Professor of Chemistry
Member of Yale faculty since 2014

E-mail: james.mayer@yale.edu
Web site: http://mayerlab.chem.yale.edu/

Research Research in the Mayer group spans the fields of inorganic, materials, bioinorganic, organometallic, and physical organic chemistry. Our primary focus is on redox reactions that involve bond formation and bond cleavage, in particular the coupled transfers of protons and electrons. Proton/electron transfers are central to a variety of important processes, from fuel cells and solar fuels to bioenergetics, from organic free radical reactions and reactive oxygen species to enzymatic oxidations, and from the properties of nanoscale metal oxides to interfacial charge transfer.

One aspect of our work is developing fundamental descriptions of the different classes of proton-coupled electron transfer (PCET) reactions. We have shown, for instance, that hydrogen atom transfers are typically well described by a model based on Marcus Theory. Studies of photo-induced PCET in phenol derivatives are probing reactions near the barrierless limit. Transition metal complexes are being synthesized with separated redox and acid/base sites, to probe the effect of separating the H+ and e–,as models for biological PCET processes. PCET principles are being applied to the development and study of electrocatalysts for small molecule transformations, such as O2 + 4H+ + 4e– Û 2H2O, which is key to fuel cell and solar fuel technologies. The Mayer group has recently shown that PCET is also a key concept in materials chemistry and interfacial charge transfer reactions. For instance metal oxide nanocrystals can transfer H+ and e– to organic reagents. The Figure below illustrates the similarity of this process with molecular separated PCET reactions.

PFe_ZnOH

The Mayer group thus works on a wide variety of systems, studying them by synthesizing new compounds, using spectroscopies of various kinds (e.g., optical, EPR, NMR), materials characterization (XRD, microscopy, NMR etc.), electrochemistry and electrocatalysis, kinetic studies including stopped-flow and laser-flash transient absorption techniques, and mechanistic studies. Cross fertilization among the different projects is stimulating for student growth and helps to develop new fundamental insights into chemical redox reactivity.

Education
A.B. Harvard University, 1978
Ph.D. California Institute of Technology, 1982

Honors
Presidential Young Investigator, National Science Foundation, 1988
Sloan Research Fellowship, Alfred P. Sloan Foundation, 1989
Polyhedron Best Paper Award, 1989
Innovation Recognition Program Awardee, Union Carbide, 1990-1991
E. Bright Wilson Prize Lecturer, Harvard University, 1992
Fellow, American Association for the Advancement of Science, 1998
Named Alvin L. and Verla R. Kwiram Professor of Chemistry at the University of Washington, 1999-2014
Chair, American Chemical Society Division of Inorganic Chemistry, 2000
Chair, Gordon Conference on Inorganic Reaction Mechanisms, 2003
E.L. King Lecturer at the University of Colorado, Boulder, 2001
Distinguished Summer Lecturer in Inorganic Chemistry, Northwestern University, 2001
Reilly Lecturer at University of Notre Dame, 2003
Inaugural Paul Hopkins Faculty Award, University of Washington, 2004
Gerhard Closs Lecturer, University of Chicago, 2007
Nakamoto Distinguished Lecture in Chemistry, Marquette University, 2010
Debye Lecturer, Cornell University, 2010
Fellow of the American Chemical Society, 2011
Distinguished Summer Lecturer in Inorganic Chemistry, Northwestern University, 2012
Dow Lecturer in Inorganic Chemistry, University of California at Berkeley, 2012
Slayton Evans Lectureship, University of North Carolina, Chapel Hill, 2013
Chair, Gordon Research Conference on Metals in Biology, 2015
Kolthoff Lecturer, University of Minnesota, Twin Cities, 2015

Recent Publications
C.N. Valdez, M. Braten, A. Soria, D.R. Gamelin, & J.M. Mayer. Effect of Protons on the Redox Chemistry of Colloidal Zinc Oxide Nanocrystals. J. Am. Chem. Soc. 2013, 135, 8492-8495. DOI: 10.1021/ja4035945.

J.J. Warren, A.R. Menzeleev, J.S. Kretchmer, T.F. Miller III, H.B. Gray, & J.M. Mayer. Long-Range Proton-Coupled Electron-Transfer Reactions of Bis(imidazole) Iron Tetraphenylporphyrins Linked to Benzoates. J. Phys. Chem. Lett. 2013, 4, 519–523. DOI: 10.1021/jz400029w.

J.N. Schrauben, R. Hayoun, C.N. Valdez, M. Braten, L. Fridley, J.M. Mayer. Titanium and Zinc Oxide Nanoparticles are Proton-Coupled Electron Transfer Agents. Science 2012, 336, 1298-1301. DOI: 10.1126/science.1220234.

J.N. Schrauben, M. Cattaneo, T.C. Day, A.L. Tenderholt, & J.M. Mayer. Multiple-Site Concerted Proton-Electron Transfer Reactions of Hydrogen-Bonded Phenols are Non-adiabatic and Well Described by Semi-Classical Marcus Theory. J. Am. Chem. Soc. 2012, 134, 16635-16645. DOI: 10.1021/ja305668h.

C.T. Carver, B.D. Matson, & J.M. Mayer. Electrocatalytic Oxygen Reduction by Iron Tetra-arylporphyrins Bearing Pendent Proton Relays. J. Am. Chem. Soc. 2012, 134, 5444-5447. DOI: 10.1021/ja211987f.

S.M. Barnett, K.I. Goldberg, & J.M. Mayer. Soluble copper-bipyridine water-oxidation electrocatalysts. Nature Chem. 2012, 4, 498-502. DOI: 10.1039/nchem.1350.

J.M. Mayer. Understanding Hydrogen Atom Transfer: from Bond Strengths to Marcus Theory. Acc. Chem. Res. 2011, 44, 36-46. DOI: 10.1021/ar100093z.

Mayer

Research Interests