Professor Jones's group is involved in the study of transition metal organometallic compounds for the cleavage of strong carbon-element bonds, with synthesis, structure, and reactivity being integral components of each project. New complexes for carrying out organometallic reactions are developed and the mechanism of the reaction is studied as a means of improving reactivity. NMR spectroscopic studies figure heavily in their work as a probe of organometallic structure.
One area that has been developed in the group over the past few years involves complexes that can activate C-H bonds of unreactive aromatic and aliphatic hydrocarbons. Through a series of kinetic studies, the relative thermodynamics of arene vs. alkane activation by the 16-electron intermediate [(trispyrazolylborate)Rh(CNR)] has been established. The studies show that alkanes first bind to the metal before undergoing cleavage of their C-H bonds, and that the metal wanders along the hydrocarbon chain before choosing which bond to break. We can also tell that methylenes bind faster than methyls.
Another area that is under active pursuit is the modeling of the hydrodesulfurization of petroleum using homogeneous complexes of rhodium. A simple, quantitative reaction has been discovered in which the C-S bond of thiophene is cleaved, giving a characterizable intermediate (see equation). Recent work has also shown that even the strong C-C bonds connecting aromatic rings can be cleaved. Studies indicate that the cleavage of 4-membered rings is facile and that cleavage of aryl-cyanide and aryl-acetylide bonds is possible using complexes of nickel, platinum, and rhodium. Catalytic hydrogenolysis of certain C-C bonds is even possible. New studies with hemi-labile P-N ligands have indicated that this approach leads to compounds with enhanced reactivities towards bond cleavage reactions. Catalytic reactions are under development. We are studying the mechanism of nickel-based allylic C-CN cleavage as it applies to the production of adiponitrile in Dupont's nylon synthesis. We have published over many papers on these topics in the last 5 years (see group website).
- Mechanistic Inorganic Chemistry and Catalysis
William D. Jones was born in Philadelphia, Pennsylvania, in 1953, and was inspired to work in inorganic chemistry as an undergraduate researcher with Mark S. Wrighton at Massachusetts Institute of Technology (BS, 1975). He obtained a Ph.D. degree in chemistry at California Institute of Technology (1979), working with Robert G. Bergman. He moved to the University of Wisconsin as an NSF postdoctoral fellow with Chuck Casey, and in 1980 accepted a position as Assistant Professor at the University of Rochester. He was promoted to Associate Professor in 1984 and Professor in 1987, and is now the Charles F. Houghton Professor of Chemistry. Professor Jones has received several awards, including an Alfred P. Sloan Research Fellowship (1984), a Camille & Henry Dreyfus Foundation Teacher-Scholar Award (1985), a Royal Society Guest Research Fellowship (1988), a Fulbright-Hays Scholar (1988), a John Simon Guggenheim Fellow (1988), the ACS Award in Organometallic Chemistry (2003), an ACS Cope Scholar Award (2009), the Royal Society of Chemistry Organometallic Chemistry Award (2017), and an Alexander von Humboldt Senior Research Award (2018). He is a Fellow of the American Association for the Advancement of Science (2009), and a Fellow of the American Chemical Society (2010). He also has served as an Associate Editor for the Journal of the American Chemical Society since 2003. Professor Jones' research interests include organometallic research in strong C-X bond cleavage, catalysis, model studies, mechanisms, kinetics, thermodynamics, and synthetic applications.
James P. Shanahan, David A. Vicic, William W. Brennessel, William D. Jones Trapping of a Late-Metal Terminal Sulfido Intermediate with Phenyl Isothiocyanate Organometallics, 2022 https://doi.org/10.1021/acs.organomet.2c00435
Mikhaila D. Ritz, William D. Jones Iron‐Catalyzed Dehydrogenation of Alcohols Using Benzoquinones as Electrochemically Regenerable Mediators European Journal of Organic Chemistry, 2022 https://doi.org/10.1002/ejoc.202200149
James Kovach, Suzanne R. Golisz, William W. Brennessel, William D. Jones Iridium(I)– and Rhodium(I)–Olefin Complexes Containing an α-Diimine Supporting Ligand Organometallics, 2022 https://doi.org/10.1021/acs.organomet.2c00036
Tim Görlich, Daniel S. Frost, Nico Boback, Nathan T. Coles, Birger Dittrich, et al. Photochemical C(sp)–C(sp2) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes LnM–C≡P Journal of the American Chemical Society, 2021 https://doi.org/10.1021/jacs.1c07370
Olaf Nachtigall, Andrew I. VanderWeide, William W. Brennessel, William D. Jones An Iron-Based Dehydration Catalyst for Selective Formation of Styrene ACS Catalysis, 2021 https://doi.org/10.1021/acscatal.1c03037
Olaf Nachtigall, Andrew I. VanderWeide, William. W. Brennessel, William D. Jones First‐Row Transition Metals Complexes with Fused Oxazolidine (FOX) Ligands Zeitschrift fÃ¼r anorganische und allgemeine Chemie, 2021 https://doi.org/10.1002/zaac.202100056
Tarah A. DiBenedetto, William D. Jones Upgrading of Ethanol to n-Butanol via a Ruthenium Catalyst in Aqueous Solution Organometallics, 2021 https://doi.org/10.1021/acs.organomet.1c00217
Thomas Auvray, Olaf Nachtigall, William W. Brennessel, William D. Jones, Ellen M. Matson Development of sterically hindered siloxide-functionalized polyoxotungstates for the complexation of 5d-metals Dalton Transactions, 2021 https://doi.org/10.1039/D1DT00256B
Tarah A. DiBenedetto, Astrid M. Parsons, William D. Jones Correction to Markovnikov-Selective Hydroboration of Olefins Catalyzed by a Copper N-Heterocyclic Carbene Complex Organometallics, 2020 https://doi.org/10.1021/acs.organomet.0c00629
Mikhaila D. Ritz, Astrid M. Parsons, Philip N. Palermo, William D. Jones Bisoxazoline-pincer ligated cobalt-catalyzed hydrogenation of alkenes Polyhedron, 2020 https://doi.org/10.1016/j.poly.2020.114416
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