Michael L. Neidig

Michael L. Neidig

Assistant Professor of Chemistry

Ph.D. 2007, Stanford University

Physical-Inorganic Chemistry and Catalysis

The research in the Neidig group focuses on the generation of new fundamental insight into structure, bonding and mechanism in homogeneous, heterogeneous and biological non-precious metal catalysts. Motivation for this research arises from the need for new catalytic routes for alternative energy applications (i.e. biomass, solar, fuel cells) as well as sustainable catalysts that are cheaper and more environmentally benign. Non-precious metal catalysts have a tremendous potential to address these significant challenges. For example, iron displays a rich redox chemistry and is inexpensive, widely available and generally non-toxic. However, in many cases, development of non-precious metal catalysts has been limited by a lack of fundamental understanding of catalyst site structure, bonding, reactivity and catalytic mechanism. A significant challenge central to this limitation is often the presence of paramagnetic starting materials or the generation of paramagnetic species along the reaction coordinate.

Central to the research in the Neidig group is the utiliztion of a physical-inorganic approach to investigate non-precious metal catalyst systems, with an emphasis on iron catalysis. Electron paramagnetic resonance (EPR) and variable-temperature, variable-field (VTVH) magnetic circular dichroism (MCD) spectroscopies combined with electronic absorption provide detailed information on the electronic structure of the metal catalysts, including metal-ligand binding and metal site geometry. The combination of these techniques, where appropriate, with resonance Raman, X-ray absorption methods and density function theory calculations yields a detailed description of the iron site structure and bonding. Importantly, this general approach is equally applicable to both ground-state structures and trapped intermediates, providing the opportunity for detailed studies on species generated along the reaction coordinate.

Current areas of interest in the group in non-precious metal catalysis include the following: (1) structure-property relationships in non-precious metal organometallics, (2) catalysis for energy applications focusing on catalytic site elucidation and mechanistic insight in non-precious metal fuel cell catalysts for oxygen reduction, and (3) electronic structure, bonding and mechanism in biologically relevant reduction catalysis including small molecule N2 fixation. The results of these research efforts will provide the necessary foundation to further advance the design and development of non-precious metal catalysts to solve key challenges in sustainable chemistry, alternative energy and non-petroleum based feedstock conversion.

Selected Publications

Dunsford, J.D., Cade, I.A., Fillman, K.L., Neidig, M.L., Ingleson, M.J.  "Reactivity of (NHC)2FeX2 complexes toward arylborane lewis acids and arlyboronates,"  Organometallics  201433370-377.
Zell, T., Milko, P. Fillman, K.L., Diskin-Posner, Y., Bendikov, T., Iron, M.A., Leitus, G., Ben-David, Y., Neidig, M.L., Milstein, D.  "Iron dicarbonyl complexes featuring bipyridine-based PNN pincer ligands with short interpyridine C-C bond lengths: Innocent of non-innocent ligand?,"  Chem. Eur. J.  2014204403-4413.
Fillman, K.L., Bielinski, E.A., Schmeier, T.J., Nesvet, J.C., Woodruff, T.M., Pan, C.J., Takase, M.K., Hazari, N., Neidig, M.L.  "Flexible binding of PNP pincer ligands to monomeric iron complexes,"  Inorg. Chem.  2014536066-6072.
Daifuku, S.L., Al-Afyouni, M.H., Snyder, B.E.R., Kneebone, J.L., Neidig, M.L.  "A combined Mossbauer, MCD and DFT approach for iron cross-coupling catalysis: Electronic structure, in situ formation and reactivity of iron-mesityl-bisphosphines,"  J. Am. Chem. Soc.  20141369132-9143.
Neidig, M.L., Clark, D.L., Martin, R.L.  "Covalency in f-element Complexes,"  Coord. Chem. Rev.  2013257394-406.
Leboeuf, D., Theiste, E., Gandon, V., Daifuku, S.L., Neidig, M.L., Frontier, A.J.  "Efficient Nazarov Cyclization/Wagner-Meerwein Rearrangement Terminated by a Cu(II)-Promoted Oxidation: Synthesis of 4-Alkylidene Cyclopentenones,"  Chem. Eur. J.  2013194842-4848.
Yoon, C.W., Hirsekorn, K.F., Neidig, M.L., Yang, X., Tilley, T.D.  "Mechanism of the decomposition of aqueous hydrogen peroxide over heterogeneous TiSBA15 and TS-1 selective oxidation catalysts: Insights from spectroscopic and density functional theory studies,"  ACS Catal.  201111665-1678.
Diebold, A.R., Brown-Marshall, C.D., Neidig, M.L., Brownlee, J.M., Moran, G.R., Solomon, E.I  "Activation of α-keto acid-dependent dioxygenases: Applications of an {FeNO}7/{FeO2}8 methodology for characterizing the initial steps of O2 activation,"  J. Am. Chem. Soc.  201113318148-18160.
Neidig, M. L., Sharma, J., Yeh, H. C., Martinez, J. S., Conradson, S. D., Shreve, A. P.   "Ag K-Edge EXAFS Analysis of DNA-Templated Fluorescent Silver Nanoclusters: Insight into the Structural Origins of Emission Tuning by DNA Sequence Variations,"  J. Am. Chem. Soc.  201113311837-11839.
Chen, X., Neidig, M. L., Tuinstra, R., Malek, A.   "Direct observation of acetyl group formation from the reaction of CO with methylated H-MOR by in situ diffuse reflectance infrared spectroscopy,"  J. Phys. Chem. Lett.  201013012-3015.
Neidig, M. L., Brown, C. D., Light, K. M., Fujimori, D. G., Nolan, E. M., Price, J. C., Barr, E. W., Bollinger, J. M., Krebs, C., Solomon, E. I.   "CD and MCD of CytC3 and taurine dioxygenase: Role of the facial triad in α-KG-dependent oxygenases,"  J. Am. Chem. Soc.  200712914224-14231.
Neidig, M. L., Wecksler, A. T., Schenk, G., Holman, T. R., Kavana, M., Solomon, E. I.  "Kinetic and spectroscopic studies of N694C lipoxygenase: A probe of the substrate activation mechanism of a nonheme ferric enzyme,"  J. Am. Chem. Soc.  20071297531-7537.
Brown, C. D., Neidig, M. L., Neibergall, M. B., Lipscomb, J. D., Solomon, E. I.  "VTVH-MCD and DFT studies of thiolate bonding in {FeNO}7/{FeNO}8 complexes of isopenicillin N synthase: Substrate determination of oxidase versus oxygenase activity in nonheme Fe enzymes,"  J. Am. Chem. Soc.  20071297427-7438.
Neidig, M. L., Decker, A., Choroba, O. W., Huang, F., Kavana, M., Moran, G. R., Spencer, J. B., Solomon, E. I.  "Spectroscopic and electronic structure studies of aromatic electrophilic attack and hydrogen-atom abstraction by non-heme iron enzymes,"  Proc. Natl. Acad. Sci. U.S.A.  200610312966-12973.
Neidig, M. L., Solomon, E. I.  "Structure-function correlations in oxygen activating non-heme iron enzymes,"  Chem. Commun.  20055843-5863.
Solomon, E. I., Neidig, M. L., Schenk, G.  "Magnetic circular dichroism of paramagnetic species,"  Comp. Coord. Chem. II   20042339-349.
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Professor Neidig's Contact Information...

Office: Hutchison B32
Phone: (585) 276-6006

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