Ph.D., 1998, Harvard University
Principal research interests include development of a general synthetic route to dithiolene ligands, synthesis of novel multiuclear dithiolene complexes as new materials, design of new, sterically hindered thiolates to support mononuclear late transition metal complexes, and development of new multidentate chiral ligands for enantioselective oxo and imido group transfer reactions to organic substrates.
I. Exploration of Improved Methods for the Preparation and Isolation of Dithiolene Ligands
Dithiolene complexes of the transition metals are well known to have many interesting and potentially very useful magnetic and photophysical properties. The further exploration and development of such applications would be greatly enhanced by improved access to alkyl- and aryl- substituted dithiolene ligands. As one of our approaches to the goal of synthesis of dithiolene ligands on a preparative scale, we are studying the base hydrolysis of phosphorus thioesters such as that illustrated below:
II. A Redox Controlled Separation of Sulfur and Nitrogen Heterocycles from Hydrocarbon Streams
Sulfur and nitrogen heterocyclic compounds, such as cyclic sulfides and pyridines, occur in crude oil streams and must be removed to prevent atmospheric pollution and to protect metal catalysts used in the refining process. Conventional hydrotreating, which uses large quantities of H2 gas, has long been the method used to deal with these molecule types. An alternative method which we are exploring is a separations based approach based on reversible binding of sulfur and nitrogen heterocycles to iron dithiolene complexes. The redox state of the iron complex is a switching mechanism that governs heterocycle binding and release.
III. Synthesis of Multinuclear Dithiolene Complexes
The deliberate synthesis of multinuclear dithiolene assemblies is a goal that has met with very limited success. We are exploring the use of benzene-1,2,4,5-tetrathiol as a bridging ligand between transition metals, as shown below. The ability to enhance and control the interesting optical, electrical, and magnetic properties found in mononuclear dithiolene complexes by synthesizing more complex systems is the goal of this research project.
IV. Chiral Sulfur Atom Transfer to Olefins
Direct sulfur atom transfer to olefins to from thiiranes is difficult to achieve. It is still more difficult to accomplish catalytically, and it has never been done enantioselectively. Enantiopure thiiranes, however, have great value as monomers for synthetic polymers with well defined properties and as building blocks in the synthesis of complex organic molecules. We are exploring molybdenum and ruthenium sulfide catalysts with chiral auxiliary ligands that will directly convert olefins to the corresponding olefin sulfides and do so with high enantioselectivity.
"Reversible, electrochemically controlled binding of phosphine to iron and cobalt bis(dithiolene) complexes", Yu, R., Arumugam, K., Manepalli, A., Tran, Y., Schmehl, R., Jacobsen, H., Donahue, J.P. (2007) Inorganic Chemistry, 46 (13), pp. 5131-5133.
"Preparation and isolation of dithiolene thiophosphoryl molecules as stable, protected forms of dithiolene ligands", Arumugam, K., Bollinger, J.E., Fink, M., Donahue, J.P. (2007) Inorganic Chemistry, 46 (8), pp. 3283-3288.
"A closer look at the hydroiodination of propiolic acid", Donahue, J.P., Synthetic Communications, 36 (23), pp. 3461-3471 (2006).
"Expanding the scope of the Newman-Kwart rearrangement - A computational assessment", Jacobsen, H., Donahue, J.P., Canadian Journal of Chemistry, 84 (11), pp. 1567-1574 (2006).
"Thermodynamic scales for sulfur atom transfer and oxo-for-sulfido exchange reactions", Donahue, J.P. Chemical Reviews, 106 (11), pp. 4747-4783 (2006).
"Facilitating access to the most easily ionized molecule: An improved synthesis of the key intermediate, W2(hpp)4Cl2, and related compounds", Cotton, F.A., Donahue, J.P., Gruhn, N.E., Lichtenberger, D.L., Murillo, C.A., Timmons, D.J., Van Dorn, L.O., Villagrán, D., Wang, X. Inorganic Chemistry, 45 (1), pp. 201-213 (2006).
"Expeditious access to the most easily ionized closed-shell molecule, W 2(hpp)4", Cotton, F.A., Donahue, J.P., Lichtenberger, D.L., Murillo, C.A., Villagrán, D., Journal of the American Chemical Society, 127 (31), pp. 10808-10809 (2005).
"Polyunsaturated Dicarboyxlate Tethers Connecting Dimolybdenum Redox and Chromophoric Centers: Absorption Spectra and Electronic Structures." Cotton, F.A.; Donahue, J. P.; Murillo, C. A.; Perez, L. M. J. Am. Chem. Soc., 2003, 125, 5486-5492.
"Polyunsaturated Dicarboxylate Tethers Connecting Dimolybdenum Redox and Chromophoric Centers: Synthesis, Structures, and Electrochemistry." Cotton, F. A.; Donahue, J. P.; Murillo, C.A.; J. Am. Chem. Soc., 2003, 125, 5436-5450.
"Quadridentate Bridging EO42- (E = S, Mo, W) Ligands and Their Role as Electronic Bridges". Cotton, F. A.; Donahue, James P.; Murillo, Carlos, A. Inorg. Chem. 2001, 40, 2229-2233.
"Synthesis and Structures of Bis(dithiolene)molybdenum Complexes Related to the Active Sites of the DMSO Reductase Enzyme Family". Lim, B. S.; Donahue, J. P.; Holm, R. H. Inorg. Chem. 2000, 39, 263-273.
"The Unperturbed Oxo-sulfido Functional Group cis-MoVIOS, Related to that in the Xanthine Oxidase Family of Molybdoenzymes: Synthesis, Structural Characterization, and Reactivity Aspects." Thapper, A.; Donahue, J. P.; Musgrave, K. B.; Willer, M. W.; Nordlander, E.; Hedman, B.; Hodgson, K. O.; Holm, R. H., Inorg. Chem. 1999, 38, 4104-4114.
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