Education
| 1977 | Ph.D. Chemistry, University of Missouri |
Professional Experience
| 1977 - 1979 | Research Associate, University of Georgia |
Brief description of research
Catalysis
Thermochemistry
Metal Complexes
Sulfur Chemistry
Kinetic Studies
Spectroscopy
The goal of our research is to understand what controls reactions important to catalysis of reactions like nitrogen fixation. Binding and activation of dinitrogen, nitriles, hydrogen, carbenes, and sulfur to metal complexes are all studied in our laboratory. Our principle focus is on molybdenum chemistry. Molybdenum is one of the most versatile of all transition metals, and also important in several enzymatic reactions--most notably a Mo/S protein complex is at the center of the active site of the nitrogenase enzyme. It is also the active metal in hydrodesulfurization to remove sulfur containing compounds from gasoline. Both nitrogen fixation, and hydrodesulfurization are of major economic and environmental importance, and there is need for improvement for both. The actual reactions are deceptively simple, but the interactions of the reactants, products, and intermediates with the metal complex catalyst is challenging and not well understood.
Nitrogen Fixation:
"catalyst"
2 N2 + 3 H2 -------------> 2 NH3
Hydrodesulfurization:
"catalyst"
RSR + 2 H2 -------------> 2 RH + H2S
Research in our group focuses on understanding catalytic interactions as well as synthesis of metal complexes of potential use in catalytic processes, both thermal and photochemical. The fundamental steps of individual steps in catalytic processes are investigated to try to understand what controls the reaction process-what barriers are involved, and how these can be lowered. A full range of techniques is used to attack these problems, including synthesis, calorimetry, high pressure infrared studies, ESR, NMR , kinetic, isotopic labeling, and collaboration with theoretical chemists. Students are trained in skills and techniques of real use in future academic, government, and industrial research.
Publications
George C. Fortman, Manuel Temprado, Tamas Kegl, Carl D. Hoff "Organometallic Radicals" (Physical Inorganic Chemistry: Applications. 2010).
Germain, M.; Temprado, M., Kryatova, O. P.; Rybak-Akimova, E. V.; Mendriatta, A.; Tsai, Y. C.; Cummins, C. C.; McDonough, J. E.; Hoff, C. D. "Ligand Binding and Reactivity Studies of [η2-N=C=NMe2]Mo([NtBu]Ar)3 Compared to [η1-N=C=NMe2]Mo([NtBu]Ar)3 --Metal Versus Ligand Based Radical Systems Depending on Organonitrile Hapticity" 15412131 (J. Am. Chem.. 2009).
George C. Fortman, Burjor Captain, Carl D. Hoff "Thermodynamic Investigations of the Staudinger Reaction of Trialkylphosphines with 1-Adamantyl Azide and the Isolation of an Unusual s-cis Phosphazide" 180848 (Inorg. Chem.. 2009).
George C. Fortman, Burjor Captain, Carl D. Hoff "Thermodynamic Investigations of the Staudinger Reaction of Trialkylphosphines with 1-Adamantyl Azide and the Isolation of an Unusual s-cis Phosphazide" 180848 (Inorg. Chem.. 2009 ).
George C. Fortman, Burjor Captain, Carl D. Hoff "Stoichiometric and Catalytic Conversion of 1-Adamantyl Azideto 1-Adamantyl Isoyanate by [Cr(CO)3Cp]2 and Reaction with Mo(CO)3(PiPR3)2 to form Mo(k-iPr3P=N-N=N-Ad)(PiPR3)(CO)3. f the Staudinger Reaction of Trialkylphosphines with 1-Adamantyl Azide and the Isolation of an Unusual s-cis Phosphazide" 358728 (Organometallics. 2009).
Patrick Achord, Manuel Temrado, George C. Fortman, Derek Isrow, John Weir, Eric McDonough, Carl D. Hoff "The Role of p-Backbonding in the Strengths of N-donor to Molybdenum Bonds. Experimental and Computational Studies of Enthalpies of Binding of Dintrogen, Diazoalkanes, Azides, Nitriles, and Pyridines to Mo(PiPr3)2(CO)3" 789148 (Inorg. Chem.. 2009).
Kelly, R. A. III, Clavier, H., Guidice, S., Scott, N, M.; Stevens, E. D.; Bordner, J.; Samardjiev, I.; Hoff, C. D.; Cavallo, L.; Nolan, S. P. "Determination of N-Heterocyclic [NHC] Stereoelectronic Parameters using the (NHC)Ir(CO)2Cl System" 20827 (Organometallics. 2008).
James E. McDonough, Arjun Mendriatta, George C. Fortman, Derek M. Isrow, Christopher C. Cummins, Elena V. Rybak-Akimova, Steven P. Nolan, and Carl D. Hoff "Thermodynamic, Kinetic, and Computational Study of Bonding to Heavier Chalcogenides in the Complexes E=Mo(NtBuAr)3 and E=NHC; E = S, Se, Te, NHC = N-Heterocyclic Carbene" 213347 (Inorg. Chem.. 2008).
George C. Fortman, Tamás Kégl, Carl D. Hoff "Kinetic, Thermodynamic, and Mechanistic Aspects of Oxidative Addition Reactions of RE-ER (E = S, Se, Te) and Transition Metal Complexes." 127912 (Topics in Current Organic Chemistry. 2008).
Manuel TempradoΦ, James Eric McDonough, Arjun Mendiratta, Yi-Chou Tsai, George C. Fortman, Christopher C. Cummins, Elena V. Rybak-Akimova, Carl D. Hoff "Thermodynamic and Kinetic Studies of H atom Transfer from H-Mo(CO)3C5H5 to Mo(N[tBu]Ar)3 and Mo(N[tBu]Ar)3(·NCPh)--Direct Insertion of Benzonitrile into the Mo-H Bond of H- Mo(N[tBu]Ar)3 forming Mo(N[tBu]Ar)3(N=C(H)Ph)" 928047 (Inorg. Chem.. 2008).
George Fortman, Derek Isrow, Eric McDonough, John Weir, Paul von Rague Schleyer, Brian Scott, Gregory J. Kubas, Ferenc Ungvary, Carl D. Hoff "Kinetic and Thermodynamic Studies of Reactivity of Trimethylsilyldiazomethane and HMo(CO)3C5R5.(R = H, Me). Estimation of the Mo-N2CH2SiMe3 Bond Strength and Experimental Determination of the Enthalpy of Formation of Trimethylsilyldiazomethane." 487347 (Organometallics. 2008).
Weir, J. J.; McDonough, J. E.; Fortman, G. C.; Isrow, D.; Hoff, C. D.; Scott, B.; Kubas, G. J. "Synthesis, Structure, and Thermochemistry of Formation of the Metal-Metal Bonded Dimers {Mo(m-TeAr)(CO)3(PiPr3)2]2 ( Ar = Ph, Napth) by Phosphine Elimination from ·Mo(TeAr)(CO)3(PiPr3)2" 65246 (Inorg. Chem.. 2007).
James T. Muckerman, Etsuko Fujita, Carl D. Hoff, and Gregory J. Kubas "Theoretical Investigation of the Binding of Small Molecules and the Intramolecular Agostic Interaction at Tungsten Centers with Carbonyl and Phosphine Ligands." 6815111 (J. Chem. Phys. B. 2007).
Fortman, G. C., Kegl, T., Li, Q. S.; Zhang, X.; Schaefer, H. F., Xie, Y.; R.; King, R. B.; Telser, J.; and Hoff, C. D "Spectroscopic Detection and Theoretical Confirmation of the Role of Cr2(CO)5(C5R5)2 and ·Cr(ketene)(CO)2(C5R5) as Intermediates in Carbonylation of N=N=CHSiMe3 to O=C=CHSiMe3 Catalyzed by ·Cr(CO)3(C5R5) (R = H, CH3)." 14389129 (J. Am. Chem. Soc.. 2007).
McDonough, J. E.; Weir, J. J.; Sukcharoenphon, K.; Hoff, C. D.; Kryatov, O. P.; Rybak-Akimova, E. V.; Scott, B.; Kubas, G. J.; Stephens, F. H.; Mendriatta, A.; Cummins, C. C "Comparison of Themodynamic and Kinetic Aspects of Dichalcogenide and Ligand Binding Reactions of Mo(CO)3(PR3)2 , W(CO)3(PR3)2, and Mo(NArR)3 Complexes. The Role of Oxidation States and Ancillary Ligands in Metal Complex Induced Chalcogenyl Radical Generation." 10295128 (J. Am. Chem. Soc.. 2006).
Mendriatta, A.; Cummins, C. C.; Kryatova, O. P.; Rybak-Akimova, E. V.; McDonough, J. E.; Hoff, C. D. "Benzonitrile Extrusion from Molybdenum (IV) Ketimide Complexes Obtained via Radical C-E ( E = O, S, Se) Bond Formation: Toward a New Nitrogen Atom Transfer Reaction" 4881128 (J. Am. Chem. Soc. 2006).
John Wiley, New York. Kiss, G., McDonough, J. E.; Weir, J. J.; Hoff, C. D "Cluster Compounds: Dinuclear Organometallic Complexes" (Encyclopedia of Inorganic Chemistry, 2nd Edition. 2005).
Dorta, R.; Stevens, E. D.; Scott, N. M.; Costabilie, C.; Carvallo, L.; Hoff, C. D.; Nolan, S. P. "Steric and Electronic Properties of N-Heterocyclic Carbenes (NHC): A Detailed Study of their Interaction with Ni(CO)4." 2485-2495127 (J. Am. Chem. Soc. 2005).
McDonough, J. E.; Carlson, M. J.; Weir, J. J.; Hoff C. D.; Kryatov, O. P.; Rybak-Akimova E. V.; Cummins C. C. "Solution Calorimetric and Stopped Flow Kinetic Studies of Reaction of Cr(CO)3C5Me5 with PhSe-SePh and PhTe-TePh. Experimental and Theoretical Estimates of the Se-Se and Te-Te Bond Strength." 312744 (Inorg. Chem.. 2005).
Stephens, F. H.; Johnson, M. J. A.; Diasconescu, P. L.; Cummins C. C., Kryatov, O. P.; Rybak-Akimova E. V, .McDonough, J. E.; Hoff C. D. "Activaiton of White Phosphorus by a Molybdaziridine-Hydride" 15191127 (J. Am.. Chem. Soc.. 2005).
Stephens, F. H.; Figueroa, J. S.; Cummins, C. C.; Kryatova, O.; Kryatov, S. V.; Rybak-Akimova, E. V.; McDonough, J. E.; Hoff, C. D. "Stephens, F. H.; Figueroa, J. S.; Cummins, C. C.; Kryatova, O.; Kryatov, S. V.; Rybak-Akimova, E. V.; McDonough, J. E.; Hoff, C. D." 3126-313823 (Organometallics. 2004).
