个人简介

Ph.D., University of Chicago, 2004 postdoctoral fellowship, University of California, Berkeley, CA (Miller Research Fellow), 2004-2006 Assistant Professor of Chemistry, University of Vermont, 2006-2012 Associate Professor of Chemistry, University of Vermont, 2012 Awards 2004-2007 - Miller Institute for Basic Research in Science Research Fellowship 2008 - National Science Foundation CAREER Award 2009 - Research Corporation Cottrell Scholar Award 2009 - Alfred P. Sloan Foundation Research Fellowship

研究领域

Inorganic, Organometallic Chemistry, Catalysis

Research in the Waterman group applies the synthesis of novel inorganic and organometallic systems to define new reactivity and catalysis. Students will have the opportunity to prepare and fully characterize new complexes through a variety of spectroscopic techniques (e.g., NMR, IR, UV-vis, EPR), X-ray crystallography, and analytical methods. These complexes are frequently air-sensitive, and students learn to manipulate the complexes using high-vacuum and Schlenk techniques or in a glovebox. These complexes will target the catalysis of chemically important processes such as bond-forming and selective oxidation reactions. A key reaction in element-element bond formation is dehydrocoupling, where two molecules with element-hydrogen bonds formally exchange E-H bonds to form E-E and H-H bonds. Dehydrocoupling is a very clean and efficient reaction taking often commercially available starting materials and providing element-element bonds with hydrogen (H2) as the only byproduct. However, for many elements this reaction is not facile, and a catalyst is needed. We have found that zirconium complexes supported by triamidoamine ligands such as (N3N = N(CH2CH2NSiMe3)33-) are effective for dehydrocoupling a range of primary and secondary phosphines. Through careful mechanistic study, we have determined that this catalysis proceeds via σ-bond metathesis steps as shown to the right. Using this knowledge we are applying this system to catalyze other element-element bond formation reactions. Using the predictive power of our sigma-bond metathesis-based mechanism, we have recently demonstrated selective P-Si and P-Ge bond formation using our zirconium catalysts, and in a simple periodic analogy, we have shown, for the first time, that catalytic dehydrocoupling of arsines is possible. Our continued efforts in this area are directed at addressing questions in molecular synthesis, materials science, and energy. A second project involves synthesis of new phosphorus-based ligand architectures to explore catalytic reactions. One reaction we are interested in is alpha-elimination, where a low-valent main group fragment (:ERm) is extruded from an early transition-metal (LnM) center such as zirconium or niobium, as depicted in the proposed catalytic cycle shown in the figure to the right. This reaction has seen limited attention in the literature, and we seek to exploit it for bond-forming catalysis. We are also interested in developing alternative routes to accessing low-valent main-group fragments. A recent development in this area is our preparation of a phosphaalkene by insertion of an isocyanide into a zirconium-phosphorus bond. In this reaction we take a commercial available phosphorus source, a primary phosphine, and access a phosphinidene (":PR") fragment with perfect atom economy.

近期论文

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Pagano, J. K.; Stelmach, J. P. W.; Waterman, R. Cobalt-Catalyzed Ammonia Borane Dehydrocoupling and Transfer Hydrogenation under Aerobic Conditions Dalton Trans. 2015 in press. Erickson, K. A., Dixon, L. S. H.; Wright, D. S., Waterman, R. Exploration of Tin-Catalyzed Dehydrocoupling: Catalyst Effects and Observation of Tin-Catalyzed: Hydrophosphination Inorg. Chim. Acta 2014, accepted. (Protagonist in Chemistry: T. Don Tilley special issue) Ghebreab, M. B.; Bange, C. A.; Waterman, R. Intermolecular Zirconium-Catalyzed Hydrophosphination of Alkenes and Dienes with Primary Phosphines J. Am. Chem. Soc. 2014, 136, 9240–9243. Erickson, K. A., Wright, D. S., Waterman, R. Dehydrocoupling of Amine Boranes via Tin(IV) and Tin(II) Catalysts J. Organomet. Chem., 2014, 751, 541–545. Part of the 50th anniversary special issue. (data) Waterman, R. sigma-Bond Metathesis: A 30-Year Retrospective Organometallics, 2013, 32, 7249-7263. Barry, B. M.; Stein, B. W.; Larsen, C. A.; Wirtz, M. N.; Geiger, W. E.; Waterman, R.; Kemp, R. A. Metal Complexes (M = Zn, Sn, and Pb) of 2-Phosphinobenzenethiolates: Insights into Ligand Folding and Hemilability Inorg. Chem., 2013, 52, 9875–9884. Maddox, A. F.; Davidson, J. J.; Shalumova, T.; Tanski, J. M.; Waterman, R. Zirconium-Mediated Synthesis of Arsaalkene Compounds from Arsines and Isocyanides Inorg. Chem., 2013, 52, 7811-7816. Waterman, R. Mechanisms of Metal-Catalyzed Dehydrocoupling Reactions Chem. Soc. Rev. 2013, 42, 5629-5641. Roering, A. J.; Elrod, L. T.; Pagano, J. K.; Guillot, S. L.; Chan, S. M.; Tanski, J. M.; Waterman, R. A General, Zirconium-Mediated Synthesis of Phosphaalkenes with Liberation of Phosphaformamides Dalton Trans. 2013, 42, 1159–1167. Elrod, L. T.; Boxwala, H.; Haq, H.; Zhao, A. W.; Waterman, R. As–As Bond Formation via Reductive Elimination from a Zirconocene Bis(Dimesitylarsenide) Compound Organometallics 2012, 31, 5304-5307. (data) Kuhune, M. E.; Waterman, R. rac-Methoxycoronaridine Hydrochloride Acta Cryst. E. 2012, 68(4), o1041. (data) Vaughan, B. A.; Wetherby A. E.; Waterman, R. Bis(p-tolyl-(2Z,4E)-4-(p-tolylimino)pent-2-en-2-yl)amino)zinc(II) Acta Cryst. E. 2012, 68(3), m343. (data) Vaughan, B. A.; Arsenault, E. A.; Chan, S. M.; Waterman, R. Synthesis and Characterization of Zinc Complexes and Testing for Phosphine Dehydrocoupling Reactivity J. Organomet. Chem. 2012, 4327-4331. Waterman, R. Dehydrogenative Bond-Forming Catalysis Involving Phosphines: Updated Through 2010 Curr. Org. Chem. 2012, 16, 1313-1331. Maddox, A. F.; Erickson, K. A.; Tanski, J. M.; Waterman, R. C–N Bond Formation via Ligand-Induced Nucleophilicity at a Coordinated Triamidoamine Ligand Chem. Commun. 2011, 11769-11771. Ghebreab, M. B.; Newsham, D. K.; Waterman, R. Differences in the Stability of Zirconium(IV) Complexes Related to Catalytic Phosphine Dehydrocoupling Reactions Dalton Trans. 2011, 40, 7683–7685. Leshinski, S. E.; Shalumova, T.; MacMillan, S. N.; Tanski, J. M.; Waterman, R. Insertion Reactions Involving a Triamidoamine-Supported Zirconium Complex Dalton Trans., 2010, 39, 9073-9078. Roering, A. J.; Leshinski, S. E.; Chan, S. M.; Shalumova, T.; MacMillan, S. N.; Tanski, J. M.; Waterman, R. Insertion Reactions and Catalytic Hydrophosphination by Triamidoamine-Supported Zirconium Complexes Organometallics, 2010, 29, 2557-2565. Ghebreab, M. B.; Shalumova, T.; Tanski, J. M.; Waterman, R. Triamidoamine-Supported Zirconium Complexes in the Catalytic Dehydrocoupling of 1,2-Bisphosphinobenzene and –Ethane Polyhedron - Young Investigator Special Issue 2010, 29, 42-45. Roering, A. J.; Maddox, A. F.; Elrod, L. T.; Chan, S. M.; Ghebreab, M. B.; Donovan, K. L.; Davidson, J. J.; Hughes, R. P.; Shalumova, T.; MacMillan, S. N.; Tanski, J. M.; Waterman, R. General Preparation of (N3N)ZrX (N3N = N(CH2CH2NSiMe3)33–) Complexes from a Hydride Surrogate Organometallics 2009, 28, 573-581.