Faculty

William D. Jones

Charles F. Houghton Professor of Chemistry
PhD, California Institute of Technology, 1979

B26 Hutchison Hall
(585) 275-5493
jones@chem.rochester.edu

Website

Research Overview

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).

Fig. 1

Selected Publications

  • “Determination of Rhodium-Alkoxide Bond Strengths in Tp¢Rh(PMe3)(OR)H,” Jing Yuwen, Yunzhe Jiao, William W. Brennessel, and William D. Jones, Inorg. Chem. 201655, 9482-9491. http://pubs.acs.org/doi/ipdf/10.1021/acs.inorgchem.6b01992
  • “Synthesis, Characterization, and Reactivities of Molybdenum and Tungsten PONOP Pincer Complexes, Sumit Chakraborty, Lloyd Munjanja, Ruth Castro Rodrigo, William W. Brennessel and William D. Jones, Organometallics, 201635, 3124–3131. http://pubs.acs.org/doi/abs/10.1021/acs.organomet.6b00461
  • “C-CN Cleavage using Palladium Supported by a Dippe Ligand,” Lloyd Munjanja, Coralys Torres-López, William W. Brennessel and William D. Jones, Organometallics 201635, 2010-2013. (NSF, CENTC, DOE) http://pubs.acs.org/doi/abs/10.1021/acs.organomet.6b00304
  • “Nitrile Coordination to Rhodium Does Not Lead to C-H Activation,” Yunzhe Jiao, William W. Brennessel, William D. Jones, Acta Cryst. C201672, 850-852. (DOE) http://scripts.iucr.org/cgi-bin/paper?S2053229616006859
  • “Towards Benchmarking in Catalysis Science: Best Practices, Opportunities and Challenges,” Thomas Bligaard, R. Morris Bullock, Charles T. Campbell, Jingguang Chen, Bruce C. Gates, Raymond J. Gorte, Christopher W. Jones, William D. Jones, John R. Kitchin, Susannah L. Scott, ACS Catal. 20166, 2590-2602. (DOE) http://pubs.acs.org/doi/abs/10.1021/acscatal.6b00183
  • “Formation of 5-Membered Metalacycles at iPrPCPIr by C-H, O-H, and C-CO Bond Cleavage,” Miles Wilklow-Marnell, William W. Brennessel, William D. Jones, Polyhedron 2016116, 38-46.  (CENTC) http://www.sciencedirect.com/science/article/pii/S0277538716001613
  • “Iron-Catalyzed Homogeneous Hydrogenation of Alkenes under Mild Conditions by a Stepwise, Bifunctional Mechanism,” Ruibo Xu, Sumit Chakraborty, Sarina M. Bellows, Hongmei Yuan, Thomas R. Cundari, and William D. Jones, ACS Catal. 20166, 2127-2135. (CENTC) http://pubs.acs.org/doi/abs/10.1021/acscatal.5b02674
  • Jones, W. D. The Effects of Ancilliary Ligands on Metal-Carbon Bond Strengths. In Topics in Organometallic Chemistry: C-H Bond Activation And Catalytic Functionalization (vol. 56); Doucet, H. and Dixneuf, P., Eds., Springer-Verlag: Berlin, 2016; pp. 67-89.  Top. Organomet. Chem.201656, 67-90.  (DOE)  doi:  10.1007/3418_2015_138   (DOE) http://link.springer.com/chapter/10.1007%2F3418_2015_138
  • “Highly Selective Formation of n-Butanol from Ethanol through the Guerbet Process: A Tandem Catalytic Approach,” Sumit Chakraborty, Paige E. Piszel, Cassandra E. Hayes, R. Tom Baker, and William D. Jones, J. Am. Chem. Soc. 2015137, 14264-14267.  (CENTC) http://pubs.acs.org/doi/abs/10.1021/jacs.5b10257
  • “Rapid Oxidative Dihydrogen Evolution from a Family of Square–Planar Nickel Hydride Complexes,” Srinivasan Ramakrishnan, Sumit Chakraborty, William W. Brennessel, and Christopher E. D. Chidsey, William D. Jones, Chem. Sci. 20167, 117-127. (GE-EFRC) http://pubs.rsc.org/En/content/articlelanding/2016/sc/c5sc03189c#!divAbstract
  • “A Single Nickel Catalyst for the Acceptorless Dehydrogenation of Alcohols and Hydrogenation of Carbonyl Compounds,” Sumit Chakraborty, Paige E. Piszel, William W. Brennessel, and William D. Jones, Organometallics201534, 5203-5206. (CENTC) http://pubs.acs.org/doi/abs/10.1021/acs.organomet.5b00824
  • “Acceptorless, Reversible Dehydrogenation and Hydrogenation of N-heterocycles with a Cobalt Pincer Catalyst,” Ruibo Xu, Sumit Chakraborty, Hongmei Yuan and William D. Jones, ACS Catalysis 20155, 6350-6354. (CETM-ESD, CENTC) http://pubs.acs.org/doi/abs/10.1021/acscatal.5b02002
  • “Mechanistic Insights in the Exchange of Arylthiolate Groups in Aryl(arylthiolato)palladium Complexes Supported by a Dippe Ligand,” Lloyd Munjanja, William W. Brennessel and William D. Jones, Organometallics 201534, 4574-4580. (NSF) http://pubs.acs.org/doi/abs/10.1021/acs.organomet.5b00662
  • “Carbon-Sulfur Bond Cleavage of Benzothiophene by Cp*Co(C2H4)2,” Natalie Hong Ting Chan, James H. Roache, and William D. Jones, Inorg. Chim. Acta2015437, 36-40. (NSF) http://www.sciencedirect.com/science/article/pii/S0020169315003904
  • “Methane is the Best Substrate for (sp3)C-H activation with Cp*(PMe3)Co(Me)(OTF). A Density Functional Theory Study,” Sarina M. Bellows, Thomas R. Cundari, and William D. Jones, Organometallics 2015, 34, 4032-4038. (CENTC) http://pubs.acs.org/doi/abs/10.1021/acs.organomet.5b00452
  • “Mechanistic Insights of a Concerted-Metalation Deprotonation Reaction with [Cp*RhCl2]2,” Aaron P. Walsh, and William D. Jones, Organometallics 201534, 3400-3407. (NSF) http://pubs.acs.org/doi/abs/10.1021/acs.organomet.5b00369
  • “Electrophilic C-H activation of benzene with a Shilov-inspired rhodium(III) diimine complex,” James Kovach, William W. Brennessel, and William D. Jones, J. Organomet. Chem. 2015793, 192-199.  (CENTC) http://www.sciencedirect.com/science/article/pii/S0022328X1500265X
  • “Room Temperature Carbon-Sulfur Bond Activation by a Reactive (dippe)Pd Fragment,” Lloyd Munjanja, William W. Brennessel and William D. Jones, Organometallics201534, 1716–1724. (NSF) http://pubs.acs.org/doi/abs/10.1021/acs.organomet.5b00194
  • “Oxidative Addition of Chlorohydrocarbons to a Rhodiumtrispyrazolylborate Complex,” Yunzhe Jiao, William W. Brennessel, and William D. Jones, Organometallics, 201534, 1552-1566.  (DOE) http://pubs.acs.org/doi/abs/10.1021/acs.organomet.5b00131
  • “Reversible Catalytic Dehydrogenation of Alcohols for Energy Storage,”  Peter J. Bonitatibus, Jr., Sumit Chakraborty, Mark D. Doherty, Oltea Siclovan, William D. Jones and Grigorii L. Soloveichik, Proc. Nat. Acad. Sci. 2015112, 1687-1692.  (CETM-ESD) https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4330783/
  • “Activation of B–H, Si–H, and C–F bonds with Tp′Rh(PMe3): Kinetics, Mechanism and Selectivity,” Barbara Procacci, Yunzhe Jiao, Meagan E. Evans, William D. Jones, Robin N. Perutz, Adrian C. Whitwood, J. Am. Chem. Soc. 2015137, 1258–1272.  (DOE) http://pubs.acs.org/doi/abs/10.1021/ja5113172
  • “Investigation of C-C Bond Activation of sp-sp3 C-C Bonds of Acetylene Derivatives via Photolysis of Pt Complexes,” Ahmet Gunay, William W. Brennessel, and William D . Jones, Organometallics 201534, 2233-2239.  (DOE) http://pubs.acs.org/doi/abs/10.1021/ja5113172
  • “Well-Defined Iron Catalysts for the Acceptorless Reversible Dehydrogenation-Hydrogenation of Alcohols and Ketones,” Sumit Chakraborty, Paraskevi O. Lagaditis, Moritz Förster, Elizabeth A. Bielinski, Nilay Hazari, Max C. Holthausen, William D. Jones and Sven Schneider, ACS Catal. 20144, 3994-4003. (CETM-ESD) doi: 10.1021/cs5009656 http://pubs.acs.org/doi/abs/10.1021/cs5009656
  • Topics in Current Chemistry, C-C Bond Activation, Guangbin Dong, Ed., “Mechanistic Studies of Transition Metal–Mediated C–C Bond Activation,” William D. Jones, Springer-Verlag: Berlin, Heidelberg, 2014, 1-32. http://link.springer.com/chapter/10.1007%2F128_2013_491
  • Addition of C-C and C-H Bonds by Pincer-Iridium Complexes: A Combined Experimental and Computational Study,” David A. Laviska, Changjian Guan, Thomas J. Emge, Miles Wilklow-Marnell, William W. Brennessel, William D. Jones, Karsten Krogh-Jespersen, Alan S. Goldman, Dalton Trans201443, 16354-16365. (DOE) http://pubs.rsc.org/en/content/articlelanding/2014/dt/c4dt02043j#!divAbstract
  • “Exploring Oxidation of Half-Sandwich Rhodium Complexes: Oxygen Atom Insertion into the Rhodium-Carbon Bond of κ2-Coordinated 2-Phenylpyridine,” Christopher R. Turlington, James Morris, Peter S. White, William W. Brennessel, William D. Jones, Maurice Brookhart, and Joseph L. Templeton, Organometallics 201433, 4442–4448. (CENTC) http://pubs.acs.org/doi/abs/10.1021/om500660n
  • “A Molecular Iron Catalyst for the Acceptorless Dehydrogenation and Hydrogenation of N-Heterocycles,” Sumit Chakraborty , William W. Brennessel , and William D. Jones, J. Am. Chem. Soc.2014136, 8564–8567. “ISI: Highly cited paper, top 1%.” (CETM-ESD) http://pubs.acs.org/doi/abs/10.1021/ja504523b
  • “Synthesis and energetics of Tp′Rh[P(OMe)3](R)H: A systematic investigation of ligand effects on C-H activation at rhodium,” Yunzhe Jiao, William W. Brennessel, and William D. Jones, Chem. Sci. 20144, 804-812. (DOE, NSF-CENTC) http://pubs.rsc.org/en/content/articlelanding/2014/sc/c3sc52748d#!divAbstract
  • “Bisindolines from the Reaction of 3,5-dimethoxyaniline with Vicinal Diones,” James Kovach, William W. Brennessel, and William D. Jones, RSC Advances 20144, 1401-1411.  (NSF-CENTC) http://pubs.rsc.org/en/content/articlelanding/2014/ra/c3ra45350b#!divAbstract