William D. Jones

William D. Jones

C.F. Houghton Professor of Chemistry

Associate Editor for J. Am. Chem. Soc.

Ph.D. 1979, California Institute of Technology

Mechanistic Inorganic Chemistry and Catalysis

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).

Selected Publications

Chakraborty, S., Brennessel, W.W., Jones, W.D.  "A Molecular Iron Catalyst for the Acceptorless Dehydrogenation and Hydrogenation of N-Heterocycles,"  J. Am. Chem. Soc.  20141368564-8567.
Jiao, Y., Brennessel, W.W., Jones, W.D.  "Synthesis and energetics of Tp′Rh[P(OMe)3](R)H: A systematic investigation of ligand effects on C-H activation at rhodium,"  Chem. Sci.  20144804-812.
Kovach, J., Brennessel, W.W., Jones, W.D.  "Bisindolines from the Reaction of 3,5-dimethoxyaniline with Vicinal Diones,"  RSC Advances  201441401-1411.
Li, J., Morris, J., Brennessel, W.W., Jones, W.D.  "Nickel(0) Addition to a Disulfide Bond,"  J. Chem. Cryst.  20134415-19.
Jiao, Y., Morries, J., Brennessel, W.W., Jones, W.D.  "Kinetic and Thermodynamic Selectivity of Intermolecular C-H Activation at [Tp′Rh(PMe3)]. How Does the Ancillary Ligand Affect the Metal-Carbon Bond Strength?,"  J. Am. Chem. Soc.  201313516198-16212.
Walsh, A.P., Brennessel, W.W., Jones, W.D.  "Synthesis and characterization of a series of rhodium, iridium, and ruthenium isocyanide complexes,"  Inorg. Chim. Acta.  2013407131-138.
Jiao, Y., Brennessel, W.W., Jones, W.D.  "A Trispyrazolylboraterbodium Phosphite Complex that Undergoes as Arbusov-Like Arrangement,"  Acta Cryst. C  2013C69939-942.
Gladysz, J. A., Ball, Z. T., Bertrand, G., Blum, S. A., Dong, V. M., Dorta, R., Hahn, F. E., Humphrey, M. G., Jones, W. D., Klosin, J., Manners, I., Marks, T. J., Mayer, J. M., Rieger, B., Ritter, J., Sattelberger, A. P., Schomaker, J. M., Yam, V. W.  "Organometallics Roundtable 2011,"  Organometallics  2012311-18.
Grochowski, M R., Brennessel, W. W., Jones, W. D.  "C-CN Bond Activation of Benzonitrile with (dippe)Rh(-1),"  Organometallics  2011305604-5610.
Kundu, S., Brennessel, W. W., Jones, W. D.  "C–S Bond Activation of Thioesters Using (dippe)Pt(NBE)2,"  Organometallics  2011305147-5154.
Tanabe, T., Evans, M. E., Brennessel, W. W., Jones, W. D.  "C-H and C-CN Bond Activation of Acetonitrile and Succinonitrile by [Tp'Rh(PR3],"  Organometallics  201130834-843.
Evans, M. E., Li, T., Jones, W. D.  "C-H vs. C-C Bond Activation of Acetonitrile and Benzonitrile via Oxidative Addition: Rhodium vs. Nickel and Cp* vs. Tp' (Tp' = hydrotris(3,5-dimethylpyrazol-1-yl)borate, Cp* = η5-pentamethylcyclopentadienyl),"  J. Am. Chem. Soc.  201013216278-16284.
Tanabe, T., Brennessel, W. W., Clot, E., Eisenstein, O., Jones, W. D.  "Synthesis, Structure, and Reductive Elimination in the Series Tp'Rh(PR3)(ArF)H; Determination of Rhodium–Carbon Bond Energies of Fluoroaryl Substituents,"  Dalton Trans.  201010495-10509.
Clot, E., Kraft, B. M., Eisenstein, O., Brennessel, W. W., Jones, W. D.  "Mechanistic Investigation of Vinylic Carbon-Fluorine Bond Activation of Perfluorinated Cycloalkenes using Cp*2ZrH2 and Cp*2ZrHF,"  J. Flourine Chem.  20101311122-1132.
Li, T., Garcia, J. J., Brennessel, W. W., Jones, W. D.  "C–CN Bond Activation of Aromatic Nitriles and Fluxionality of the η2-Arene Intermediates: Experimental and Theoretical Investigations,"  Organometallics  2010292430-2445.
Gunay, A., Müller, C., Lachicotte, R. J., Brennessel, W. W., Jones, W. D.  "Reactivity Differences of Pt0 Phosphine Complexes in C–C Bond Activation of Asymmetric Acetylenes,"  Organometallics  2009286524-6530.
Evans M. E., Burke, C. L., Yaibuathes, S., Clot, E., Eisenstein, O., Jones, W. D.  "Energetics of C-H Bond Activation of Fluorinated Aromatic Hydrocarbons Using a [Tp ' Rh(CNneopentyl)] Complex,"  J. Am. Chem. Soc.  200913113464-13473.
Torres-Nieto, J., Brennessel, W. W., Jones, W. D., García, J. J.  "Mechanistic Insights on the Hydrodesulfurization of Biphenyl-2-Thiol with Nickel Compounds,"  J. Am. Chem. Soc.  20091314120-1426.
Vetter, A. J., Rieth, R. D., Brennessel, W. W., Jones, W. D.   "Selective C–H Activation of Haloalkanes using a Rhodiumtrispyrazolylborate Complex,"  J. Am. Chem. Soc.  200913110742-10752.
Wick, D. D., Jones, W. D.  "Synthesis, Characterization, and C–H/C–C Cleavage Reactions of Two Rhodium-Trispyrazolylborate Dihydrides,"  Inorg. Chim. Acta  2009124416-4421.
Li, L., Brennessel, W. W., Jones, W. D.  "C-H Activation of Phenyl Imines and 2-Phenylpyridines with [Cp*MCl2]2 (M) Ir, Rh: Regioselectivity, Kinetics, and Mechanism,"  Organometallics  2009283492-3500.
Grochowski, M. R., Brennessel, W. W., Jones, W. D.  "Carbon-Sulfur Bond Cleavage of Methyl Substituted Thiophenes with Iridium(III),"  Organometallics  2009282661-2667.
Acosta-Ramírez, A., Flores-Álamo, M., Jones, W. D., García, J. J.  "P-C bond scission at the TRIPHOS ligand and C-CN bond cleavage in 2-methyl-3-butenenitrile using [Ni(COD)2],"  Organometallics  2008271834-1840.
Ateşin, T. A., Ateşin, A. C., Skugrud, K., Jones, W. D.  "Understanding Selectivity in the Oxidative Addition of the Carbon-Sulfur Bonds of 2-Cyanothiophene to Pt(0),"  Inorg. Chem.  2008474596-4604.
Swartz, B. D., Brunkan, N. M., Garcia, J. J., Jones, W. D.  "Solvent Effects and Eyring Activation Parameters of the Competitive Cleavage of C-CN and C-H Bonds in 2-Methyl-3-Butenenitrile Using [(dippe)NiH]2,"  J. Am. Chem. Soc.  20081308548-8554.
Ateşin, T. A., Li, T., Lachaize, S., García, J. J., Jones, W. D.  "Experimental and Theoretical Examination of C–CN Bond Activation of Benzonitrile using Zerovalent Nickel,"  Organometallics  2008273811-3817.
Clot, E., Eisenstein, O., Jones, W. D.  "Structural and Dynamic Properties of Propane Coordinated to TpRh(CNR) from a Comparison between DFT and Experiment Results,"  Proc. Nat. Acad. Sci.  20071046939-6944.
Vetter, A. J., Rieth, R. R., Jones, W. D.  "The Activation of Alkyl Cyanides Using a Rhodiumtrispyrazolylborate Complex,"  Proc. Nat. Acad. Sci.  20071046957-6962.
Vetter, A. J., Flaschenriem, C., Jones, W. D.  "Alkane Coordination Selectivity in Hydrocarbon Activation by [Tp'Rh(CNneopentyl)]: The Role of Alkane Complexes,"  J. Am. Chem. Soc.  200512712315-12322.
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Professor Jones's Contact Information...

Office: Hutchison B26
Phone: (585) 275-5493

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