Thomas B. Rauchfuss
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.
Research
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 C—S bond cleavage (to separate the sulfur from the organic matrix) and the synthesis of novel compounds as catalysts. A key aspect of C—S 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.
Publications
Chen, J.; Boyke, C.; Rauchfuss, T. B.; Volkers, P. I.; Whaley, C. M.; Wilson, S. R.; Yao, H. "Precursors to [FeFe]-Hydrogenase Models: Syntheses of Fe2(SR)2(CO)6 from CO-Free Iron Sources" submitted 4/08
"Nitrosyl Derivatives of Diiron(I) Dithiolates Mimic the Structure and Lewis Acidity of the FeFe-Hydrogenase Active Site" Olsen, M. T.; Bruschi, M.; De Gioia, L.; Rauchfuss, T. B.; Wilson, S. R. submitted for publication 3/08.
"Redox and Structural Properties of Models for the Hox State of the [FeFe]-Hydrogenase: Progress and Challenges" Justice, A. K.; De Gioia, L.; Nilges, M. J.; Rauchfuss, T. B.; Wilson, S. R.; Zampella, G. submitted for publication 3/08.
"Terminal Hydride in [FeFe]-Hydrogenase Model Has Lower Potential for H2 Production than the Isomeric Bridging Hydride" Barton, B. E.; Rauchfuss, T. B. Inorg. Chem. 2008, 47, ASAP.
"Supramolecular Architectures Based on Organometallic Half-sandwich Complexes" Rauchfuss, T. B.; Severin, K. in "Molecular Nanostructures" Atwood, J.; Steed, J. eds. Wiley-VCH, 2008; pp. 179-201.
"Desulfurization of Petroleum Streams Utilizing Multi-Ring Aromatic Alkali Metal Complex", Siskin, M.; Myers, R. D.; Beardon, R.; Rauchfuss, T. B. U. S. Patent filed November, 2007, assigned to ExxonMobil.
"Expanded Cyanometallate Cages Derived from Dimetallic Dicyanide Building Blocks: {[Cp*Rh]4[Fe2(S2C3H6)(CN)2(CO)4]6}4-"Boyer, J. L.; Rauchfuss, T. B.; Wilson, S. R. Comptes Rendus 2008, in press (special edition on hydrogenase models).
"Lewis Base Adducts Derived from Transfer Hydrogenation Catalysts: Scope and Selectivity" Heiden, Z. M.; Gorecki, B. J.; Rauchfuss, T. B. Organometallics, 2008, 27, 1542-1549.
"Diiron Dithiolato Carbonyls Related to HoxCO State of [FeFe]-Hydrogenase" Justice, A. K.; Nilges, M. A.; Rauchfuss, T. B.; Wilson, S. R.; De Gioia, L.; Zampella, G., J. Am Chem. Soc. 2008, 130, ASAP.
"Characterization of the Fe Site in Methanothermobacter marburgensis Hydrogenase (mHmd) via Nuclear Resonant Vibrational Spectroscopy (NRVS)" Guo, Y.; Wang, H.; Xiao, Y.; Vogt, S.; Thauer, R. K.; Shima, S.; Rauchfuss, T. B.; Volkers, P. I.; Alp, E.; Sturhahn, W.; Yoda, Y.; Cramer, S. P. Inorg. Chem. 2008, 47, 0000-0000.
"Coordination Chemistry of a Model for the GP Cofactor in the Hmd Hydrogenase: Hydrogen-Bonding and Hydrogen-Transfer Catalysis" Royer, A. M.; Rauchfuss, T. B.; Wilson, S. R. Inorg. Chem., 2008, 47, 395-397.
"Desymmetrized Diiron Azadithiolates: A Step Toward Modeling the Fe-only Hydrogenases" Stanley, J. L.; Heiden, Z. M.; Rauchfuss, T. B.; Wilson, S. R.; De Gioia, L.; Zampella, G. Organometallics 2008, 27, 119-125.
"Redox-Switched Oxidation of Dihydrogen using a Non-innocent Ligand" Ringenberg, M. R.; Kokatam, S. L.; Heiden, Z. M.; Rauchfuss, T. B. J. Am. Chem. Soc., 2008, 130, 788-789.
"Extending the FeFe-Hydrogenase Motif: Protonation of Fe2(NR2)2L6", P. I. Volkers, T. B. Rauchfuss, J. Inorg. Biochem. (Stiefel Memorial Issue) 2007, 101, 1748-1751.
"Homogeneous Catalytic Reduction of Dioxygen Using Transfer Hydrogenation Catalysts", Z. M. Heiden and T. B. Rauchfuss, J. Am. Chem. Soc., 2007, 129, 14303-14310.
"Unsaturated Mixed Valence Diiron Dithiolate Model for the Hox State of the [FeFe]-Hydrogenase", A. K. Justice, T. B. Rauchfuss, S. R. Wilson, Angew. Chem. Int. Ed., 2007, 46, 6152-6154.
"Lewis vs BrØnsted-Basicities of Diiron Dithiolates: Spectroscopic Detection of the "Rotated Structure" and Remarkable Effects of Ethane- vs. Propanedithiolate" Justice, A. K.; Zampella, G.; De Gioia, L.; Rauchfuss, T. B. Chem. Commun., 2007, 2019-21.
"Cyanometallate Cages with Exchangeable Terminal Ligands" Boyer, J. L.; Yao, H.; Kuhlman, M. L.; Rauchfuss, T. B.; Wilson, S. R. (invited paper for 10th anniversary issue) Eur. J. Inorg. Chem. 2007, 2721-2728.
"Studies on the Condensation Pathway to and Properties of Diiron Azadithiolate Carbonyls" Stanley, J. L.; Rauchfuss, T. B.; Wilson, S. R. Organometallics, 2007, 26, 1907-1911.
"Evolution of Organo-Cyanometallate Cages: Supramolecular Architectures and New Cs+-Specific Receptors" Boyer, J. L.; Kuhlman, M. L.; Rauchfuss, T. B. Accts Chem. Rsch. 2007, 40, 233-242.
"Chelate Control of Diiron(I) Dithiolates Relevant to the Fe-only Hydrogenase Active Site" Justice, A. K.; Zampella, G.; De Gioia, L.; van der Vlugt, J. I.; Rauchfuss, T. B. Inorg. Chem. 2007, 46, 1655-1664.
"Redox-Switched Complexation/Decomplexation of K+ and Cs+ by Molecular Cyanometalate Boxes" Boyer, J. L.; Ramesh, M.; Yao, H.; Rauchfuss, T. B.; Wilson, S. R.; J. Am. Chem. Soc. 2007, 129, 1931 -1936.
Awards
- 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
