Thomas B. Rauchfuss
Larry Faulkner Professor of Chemistry
Professor Thomas B. Rauchfuss received his undergraduate degree from the University of Puget Sound (1971) and his Ph.D. from Washington State University (1976). He has studied overseas at the following institutions: the Australian National University, University of Auckland, University of Strasbourg, and the Technical University of Karlsruhe. He is interested in all aspects of the synthesis and reactivity of inorganic, organometallic, and main-group compounds and materials.
We are interested in all aspects of the synthesis and reactivity of inorganic, organo-metallic, and main-group compounds and materials.
A major interest for our group is environmentally-motivated organometallic chemistry. We are interested in fundamental studies leading to clean fuels. One aspect of this research is the elucidation of nature's methods for making H2, which involves the use of unusual and poorly understood enzymes called hydrogenases. We are working to simulate a range of curious structural features in these enzymes. Other interests include the role of metals in nitrogen fixation, carbonylation enzymes, and methanogenesis.
Because most energy is generated from petroleum, we are interested in new catalysts for removing sulfur from this feedstock. Fundamental issues include the detailed mechanisms of CS bond cleavage (to separate the sulfur from the organic matrix) and the synthesis of novel compounds as catalysts. A key aspect of CS bond cleaving reactions is the role of H2. One can appreciate that studies on bioinorganic and industrial chemistry overlap significantly, and we feel there are important lessons to be exchanged between these otherwise disparate themes.
Another area of interest is the design of organometallic boxes, bowls, and tubes. These fundamental structures represent the ultimate nanoscale containers, but rational routes for their synthesis represent a frontier of synthesis. Representative products of this effort are a rhodium-containing bowl based on seven Rh atoms interconnected by nine cyanides, molecular boxes with metals at the corners. The molecular boxes selectively bind alkali metals (at their center) such that the binding of Cs+ is favored over the binding of K+ by more than 104-fold. This selectivity illustrates the advantages of the rigid frameworks versus the usual organic heterocyclic ligands. We are making progress in the synthesis of electroactive cages for sensors and in understanding and controlling the cage assembly processes.
“Combining Acid-Base, Redox, and Substrate Binding Functionalities to Give a Complete Model for the [FeFe]-Hydrogenase” Camara, J. M.; Rauchfuss, T. B. Nature-Chem. 2012, 4, 26–30.
“Protonation-Enhanced Lewis Acidity of Iridium Complexes Containing Non-Innocent Amidophenolates” Ringenberg, M. R.; Rauchfuss, T. B. Eur. J. Inorg. Chem. 2012, 490-495.
“Influence of Second Coordination Sphere Hydroxyl Groups on the Reactivity of Copper(I) Complexes” Letko, C. S.; Rauchfuss, T. B.; Gray, D. L.; Zhou, X. Inorg. Chem. 2012, 51, 4511–4520.
"Mixed-Valence Nickel-Iron Dithiolates Models of the [NiFe]-Hydrogenase Active Site” Schilter, D.; Nilges, M. J.; Chakrabarti, M.; Lindahl, P. A.; Rauchfuss, T. B.; Stein, M. Inorg. Chem. 2012, 51, 2338−2348.
"Unsensitized Photochemical Hydrogen Production Catalyzed by Diiron Hydrides" Wang, W.; Rauchfuss, T. B.; Bertini, L.; Zampella, G. J. Am Chem. Soc. 2012, 134, 4525-4528.
"Reaction of Aryl Diazonium Salts and Diiron(I) Dithiolato Carbonyls: Evidence for Radical Intermediates" Olsen, M. T.; Rauchfuss, T. B.; Zaffaroni, R. Organometallics, 2012, 31, 3447−3450.
"Connecting [NiFe]- and [FeFe]-Hydrogenases: Mixed-Valence Nickel-Iron Dithiolates with Rotated Structures" Schilter, D.; Rauchfuss, T. B.; Stein, M. Inorg. Chem. 2012, 51, 8931−8941.
"EPR/ENDOR, Mössbauer, and Quantum Chemical Investigation of Di-iron Complexes Mimicking the Active Oxidized State of [FeFe] Hydrogenase" Silakov, A.; Olsen, M. T.; Sproules, S.; Reijerse, E.; Rauchfuss, T. B.; Lubitz, W. Inorg. Chem. 2012, 51, 8617−8628.
"C2-Symmetric Iron(II) Diphosphine-Dialkoxide Dicarbonyl and Related Complexes" Lei, H.; Royer, A. M.; Rauchfuss, T. B.; Gray, D. L. Organometallics, 2012, 31, 6408–6414.
"Nickel-Iron Dithiolates Related to Deactivated [NiFe]-Hydrogenases" Schilter, D.; Rauchfuss, T. B. Dalton Trans. 2012, 41, 13324-13329.
"Synthetic Models for the [FeFe]-Hydrogenase: Catalytic Proton Reduction and the Structure of the Doubly Protonated Intermediate" Carroll, M. E.; Barton, B. E.; Rauchfuss, T. B.; Carroll, P. J. J. Am Chem. Soc. 2012, 134,18843−18852.
"Regiochemistry of Protonation of the [FeFe]-Hydrogenase Models of the Type Fe2(dithiolate)(CO)2(PMe3)4" Zaffaroni, R.; Rauchfuss, T. B.; Gray, D.; De Gioia, L.; Zampella, G. J. Am. Chem. Soc., 2012, 134, 19260−19269.
"Active Site Fe-CN and Fe-CO Vibrations in [NiFe] Hydrogenase – Observation by Nuclear Resonance Vibrational Spectroscopy " Kamali, S.; Wang, H.; Mitra, D.; Ogata, H.; Lubitz, W.; Mack, A. E.; Rauchfuss, T. B.; Bonnefoy, V.; Jenney, Jr., F. E.; Yoda, Y.; Alp, E.; Zhao, J.; Cramer, S. P. Angew. Chem. Int. Ed. 2013, 52, 724-728.
"Production of Hybrid Diesel Fuel Precursors from Carbohydrates and Petrochemicals Using Formic Acid as a Reactive Solvent" Zhou, X.; Rauchfuss, T. B. ChemSusChem 2013, 6, 383-388.
"Ligand Effects on the Overpotential for Dioxygen Reduction by tris(2-Pyridylmethyl)amine Derivatives" Thorseth, M. A.; Letko, C. S.; Tse, E.; Rauchfuss, T. B.; Gewirth, A. A. Inorg. Chem. 2013, 52, 628-634
"Diphosphido- vs Dithiolato-Diiron(I) Carbonyls as Models for Active Site of the [FeFe]-Hydrogenase" Zaffaroni, R.; Rauchfuss, T. B.; De Gioia, L.; Zampella, G. Organometallics, 2013, 32, 232−238.
"Isolation of a Mixed Valence Diiron Hydride: Evidence for a Spectator Hydride in Hydrogen Evolution Catalysis" Wang, W.; Nilges, M. J.; Rauchfuss, T. B.; Stein, M. J. Am. Chem. Soc., 2013, 135, 3633–3639.
- Ronald Nyholm Prize, Royal Society of Chemistry
- Fellow, American Chemical Society
- ACS Award in Inorganic Chemistry
- Fellow, Japan Society for the Promotion of Science
- Humboldt Foundation Senior Scientist
- Guggenheim Fellowship
- University of Illinois Scholar
- Alfred P. Sloan Fellowship
- Dreyfus Teacher-Scholar Award
- Union Carbide Innovative Recognition Award
- DuPont Young Professor Award