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R

R Morris Bullock

Catalysis Science
Laboratory Fellow
Pacific Northwest National Laboratory
PO Box 999
MSIN: K2-57
Richland, WA 99352

Biography

Morris Bullock is the Director of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center. He is a Laboratory Fellow, he is currently located in the Catalysis Sciences Group in the Physical Sciences Division at Pacific Northwest National Laboratory. From 1985-2006, he was in the Chemistry Department at Brookhaven National Laboratory (Long Island, New York).

Research Interests

  • Research in the Center for Molecular Electrocatalysis focuses on the development of molecular transition metal electrocatalysts for multi-proton, multi-electron reactions that are needed for a secure energy future. Our research seeks to understand how proton relays can regulate the movement of protons and electrons to enhance the rates of electrocatalysts. Proton relays are typically pendant amines in the second coordination sphere of the metal catalyst. The focus of our studies are on catalysts for oxidation of hydrogen and production of hydrogen through reduction of protons. New studies focus on approaches to reduction of nitrogen to ammonia.
  • Research interests include synthetic, kinetic, and mechanistic aspects of transition metal organometallic complexes and their use as homogeneous catalysts. Much of his work focuses on the reactivity of metal hydrides, and the factors that influence the cleavage of the M-H bond as a proton, a hydride, or a hydrogen atom.
  • He and his co-workers have been interested for many years in the development of catalysts based on abundant, inexpensive metals as alternatives to the widespread use of precious metals ("Cheap Metals for Noble Tasks"). They have developed homogeneous hydrogenation catalysts that are based on molybdenum or tungsten. These catalysts function through an ionic hydrogenation mechanism, in which H2 is added to the C=O bond of a ketone by H+ transfer from a cationic dihydride complex, followed by H- transfer from a neutral metal hydride. Related interests include development of new catalysts for hydrosilylation, use of alternative resources as feedstock, and readily recyclable catalysts.
  • In addition to these studies that focus on heterolytic bond cleavage pathways (proton and hydride transfers), studies are also being carried out on fundamental aspects of homolytic bond cleavage reactions. While metal-to-carbon hydrogen atom transfers are well-known, few studies have focused on the opposite reaction, carbon-to-metal hydrogen atom transfer. We have discovered examples in which such reactions can be directly observed by time-resolved infrared spectroscopy. Our studies seek to address fundamental questions about the thermodynamics and kinetics of these reactions.

Education and Credentials

  • B.S., Chemistry, University of North Carolina at Chapel Hill, 1979
  • Ph.D., Chemistry, University of Wisconsin-Madison, 1984 (Chuck Casey's group)
  • Postdoctoral Research Associate with Prof. Jack Norton at Colorado State University (1984-1985)

Awards and Recognitions

PNNL Publications

2014

  • Bullock RM, AM Appel, and ML Helm. 2014. "Production of Hydrogen by Electrocatalysis: Making the H-H Bond by Combining Protons and Hydrides." Chemical Communications 50(24):3125-3143.  doi:10.1039/c3cc46135a
  • Chen S, MH Ho, RM Bullock, DL DuBois, M Dupuis, RJ Rousseau, and S Raugei. 2014. "Computing Free Energy Landscapes: Application to Ni-based Electrocatalysts with Pendant Amines for H2 Production and Oxidation." ACS Catalysis 4(1):229-242.  doi:10.1021/cs401104w
  • Das PP, MH Ho, MJ O'Hagan, WJ Shaw, RM Bullock, S Raugei, and ML Helm. 2014. "Controlling Proton Movement: Electrocatalytic Oxidation of Hydrogen by a Nickel(II) Complex Containing Proton Relays in the Second and Outer Coordination Spheres." Dalton Transactions 43(7):2744-2754.  doi:10.1039/c3dt53074d
  • Heiden ZM, S Chen, LAN Labios, RM Bullock, ED Walter, EL Tyson, and MT Mock. 2014. "Proton and Electron Additions to Iron (II) Dinitrogen Complexes Containing Pendant Amines." Organometallics 33(6):1333-1336.  doi:10.1021/om401089d
  • Lewandowska-Androlojc A, DC Grills, J Zhang, RM Bullock, A Miyazawa, Y Kawanishi, and E Fujita. 2014. "Kinetic and Mechanistic Studies of Carbon-to-Metal Hydrogen Atom Transfer Involving Os-Centered Radicals: Evidence for Tunneling." Journal of the American Chemical Society 135(9):3572-3578.  doi:10.1021/ja4123076
  • Liu TL, X Wang, C Hoffmann, DL DuBois, and RM Bullock. 2014. "Heterolytic Cleavage of Hydrogen by an Iron Hydrogenase Model: An Fe-H - - - H-N Dihydorgen Bond Characterized by Neutron Diffraction." Angewandte Chemie International Edition 53(21):5300-5304.  doi:10.1002/anie.201402090
  • Weiss CJ, JD Egbert, S Chen, ML Helm, RM Bullock, and MT Mock. 2014. "Protonation Studies of a Tungsten Dinitrogen Complex Supported by a Diphosphine Ligand Containing a Pendant Amine." Organometallics 33(9):21859-2200.  doi:10.1021/om401127v

2013

  • Bullock RM. 2013. "Abundant Metals Give Precious Hydrogenation Performance." Science 342(6162):1054-1055.  doi:10.1126/science.1247240
  • Das AK, MH Engelhard, F Liu, RM Bullock, and JA Roberts. 2013. "The Electrode as Organolithium Reagent: Catalyst-Free Covalent Attachment of Electrochemically Active Species to an Azide-Terminated Glassy Carbon Electrode Surface." Inorganic Chemistry 52(23):13674-13684.  doi:10.1021/ic402247n
  • Roberts JA, and RM Bullock. 2013. "Direct Determination of Equilibrium Potentials for Hydrogen Oxidation/Production by Open Circuit Potential Measurements in Acetonitrile." Inorganic Chemistry 52(7):3825-3835.  doi:10.1021/ic302461q
  • van der Eide EF, GL Hou, S Deng, H Wen, P Yang, RM Bullock, and XB Wang. 2013. "Metal-Centered 17-Electron Radicals CpM(CO)3· (M = Cr, Mo, W): A Combined Negative Ion Photoelectron Spectroscopic and Theoretical Study." Organometallics 32(7):2084-2091.  doi:10.1021/om3011454
  • van der Eide EF, ML Helm, ED Walter, and RM Bullock. 2013. "Structural and Spectroscopic Characterization of 17- and 18-Electron Piano-Stool Complexes of Chromium. Thermochemical Analyses of Weak Cr-H Bonds." Inorganic Chemistry 52(3):1591-1603.  doi:10.1021/ic302460y
  • van der Eide EF, P Yang, and RM Bullock. 2013. "Isolation of Two Agostic Isomers of an Organometallic Cation: Different Structures and Colors." Angewandte Chemie International Edition 52(39):10190-10194.  doi:10.1002/anie.201305032
  • Franz JA, MJ O'Hagan, MH Ho, TL Liu, ML Helm, S Lense, DL DuBois, WJ Shaw, AM Appel, S Raugei, and RM Bullock. 2013. "Conformational Dynamics and Proton Relay Positioning in Nickel Catalysts for Hydrogen Production and Oxidation." Organometallics 32(23):7034-7042.  doi:10.1021/om400695w
  • Heiden ZM, S Chen, MT Mock, WG Dougherty, WS Kassel, RJ Rousseau, and RM Bullock. 2013. "Protonation of Ferrous Dinitrogen Complexes Containing a Diphosphine Ligand with a Pendant Amine ." Inorganic Chemistry 52(7):4026-4039.  doi:10.1021/ic4000704
  • Ho MH, S Chen, RJ Rousseau, M Dupuis, RM Bullock, and S Raugei. 2013. "Bio-Inspired Molecular Catalysts for Hydrogen Oxidation and Hydrogen Production." Chapter 6 in Application of Molecular Modeling to Challenges in Clean Energy. ACS Symposium Series, vol. 1133, ed. G Fitzgerald and N Govind, pp. 89-111.  American Chemical Society, Washington, DC. 
  • Ho MH, S Raugei, RJ Rousseau, M Dupuis, and RM Bullock. 2013. "Evaluation of the Role of Water in the H2 Bond Formation by Ni(II)-based Electrocatalysts ." Journal of Chemical Theory and Computation 9(8):3505-3514.  doi:10.1021/ct400396s
  • Hoffert WA, JA Roberts, RM Bullock, and ML Helm. 2013. "Production of H2 at Fast Rates Using a Nickel Electrocatalyst in Water/Acetonitrile Solutions." Chemical Communications 49(71):7767-7769.  doi:10.1039/c3cc43203c
  • Hulley EB, KD Welch, AM Appel, DL DuBois, and RM Bullock. 2013. "Rapid, Reversible Heterolytic Cleavage of Bound H2." Journal of the American Chemical Society 135(32):11736-11739.  doi:10.1021/ja405755j
  • Liu TL, DL DuBois, and RM Bullock. 2013. "An iron complex with pendant amines as a molecular electrocatalyst for oxidation of hydrogen." Nature Chemistry 5(3):228-233.  doi:10.1038/NCHEM.1571
  • Mock MT, S Chen, MJ O'Hagan, RJ Rousseau, WG Dougherty, WS Kassel, and RM Bullock. 2013. "Dinitrogen Reduction by a Chromium(0) Complex Supported by a 16-membered Phosphorus Macrocycle." Journal of the American Chemical Society 135(31):11493-11496.  doi:10.1021/ja405668u
  • Stewart MP, II, MH Ho, S Wiese, ML Lindstrom, CE Thogerson, S Raugei, RM Bullock, and ML Helm. 2013. "High Catalytic Rates for Hydrogen Production Using Nickel Electrocatalysts with Seven-Membered Diphosphine Ligands Containing One Pendent Amine." Journal of the American Chemical Society 135(16):6033-6046.  doi:10.1021/ja400181a
  • Wiedner ES, AM Appel, DL DuBois, and RM Bullock. 2013. "Thermochemical and Mechanistic Studies of Electrocatalytic Hydrogen Production by Cobalt Complexes Containing Pendant Amines." Inorganic Chemistry 52(24):14391-14403.  doi:10.1021/ic4025475
  • Wiedner ES, JA Roberts, WG Dougherty, WS Kassel, DL DuBois, and RM Bullock. 2013. "Synthesis and Electrochemical Studies of Cobalt(III) Monohydride Complexes Containing Pendant Amines." Inorganic Chemistry 52(17):9975-9988.  doi:10.1021/ic401232g
  • Wiese S, UJ Kilgore, MH Ho, S Raugei, DL DuBois, RM Bullock, and ML Helm. 2013. "Hydrogen Production using Nickel Electrocatalysts with Pendant Amines: Ligand Effects on Rates and Overpotentials." ACS Catalysis 3(11):2527-2535.  doi:10.1021/cs400638f
  • Yang JY, SE Smith, TL Liu, WG Dougherty, WA Hoffert, WS Kassel, M Rakowski DuBois, DL DuBois, and RM Bullock. 2013. "Two Pathways for Electrocatalytic Oxidation of Hydrogen by a Nickel Bis(diphosphine) Complex with Pendant Amines in the Second Coordination Sphere." Journal of the American Chemical Society 135(26):9700-9712.  doi:10.1021/ja400705a

2012

  • van der Eide EF, P Yang, ED Walter, TL Liu, and RM Bullock. 2012. "Dinuclear Metalloradicals Featuring Unsupported Metal-Metal Bonds." Angewandte Chemie International Edition 51(33):8361-8364.  doi:10.1002/anie.201203531
  • van der Eide EF, TL Liu, DM Camaioni, ED Walter, and RM Bullock. 2012. "Facile Thermal W-W Bond Homolysis in the N-Heterocyclic Carbene-Containing Tungsten Dimer [CpW(CO)2(IMe)]2." Organometallics 31(5):1775-1789.  doi:10.1021/om201162g
  • Liu TL, S Chen, MJ O'Hagan, M Rakowski DuBois, RM Bullock, and DL DuBois. 2012. "Synthesis, Characterization and Reactivity of Fe Complexes Containing Cyclic Diazadiphosphine Ligands: The Role of the Pendant Base in Heterolytic Cleavage of H2 ." Journal of the American Chemical Society 134(14):6257-6272.  doi:10.1021/ja211193j
  • O'Hagan MJ, MH Ho, JY Yang, AM Appel, M Rakowski DuBois, S Raugei, WJ Shaw, DL DuBois, and RM Bullock. 2012. "Proton Delivery and Removal in [Ni(PR2NR'2)2]2+ Hydrogen Production and Oxidation Catalysts." Journal of the American Chemical Society 134(47):19409-19424.  doi:10.1021/ja307413x
  • Raugei S, S Chen, MH Ho, B Ginovska-Pangovska, RJ Rousseau, M Dupuis, DL DuBois, and RM Bullock. 2012. "The Role of Pendant Amines in the Breaking and Forming of Molecular Hydrogen Catalyzed by Nickel Complexes." Chemistry - A European Journal 18(21):6493-6506.  doi:10.1002/chem.201103346
  • Weiss CJ, AN Groves, MT Mock, WG Dougherty, WS Kassel, ML Helm, DL DuBois, and RM Bullock. 2012. "Synthesis and reactivity of molybdenum and tungsten bis(dinitrogen) complexes supported by diphosphine chelates containing pendant amines." Dalton Transactions 41(15):4517-4529.  doi:10.1039/C2DT12224C
  • Wiedner ES, JY Yang, S Chen, S Raugei, WG Dougherty, WS Kassel, ML Helm, RM Bullock, M Rakowski DuBois, and DL DuBois. 2012. "Stabilization of Nickel Complexes with Ni0···H-N Bonding Interactions Using Sterically Demanding Cyclic Diphosphine Ligands." Organometallics 31(1):144-156.  doi:10.1021/om200709z
  • Wiese S, UJ Kilgore, DL DuBois, and RM Bullock. 2012. "[Ni(PMe2NPh2)2](BF4)2 as an Electrocatalyst for H2 Production." ACS Catalysis 2(5):720-727.  doi:10.1021/cs300019h

2011

  • Bullock RM. 2011. "A Mercurial Route to a Cobalt Dihydrogen Complex." Angewandte Chemie International Edition 50(18):4050-4052.  doi:10.1002/anie.201006731
  • DuBois DL, and RM Bullock. 2011. "Molecular Electrocatalysts for the Oxidation of Hydrogen and the Production of Hydrogen - The Role of Pendant Amines as Proton Relays." European Journal of Inorganic Chemistry 2011(7):1017-1027.  doi:10.1002/ejic.201001081
  • Appel AM, DH Pool, MJ O'Hagan, WJ Shaw, JY Yang, M Rakowski DuBois, DL DuBois, and RM Bullock. 2011. "[Ni(PPh2NBn2)2(CH3CN)]2+ as an Electrocatalyst for H2 Production: Dependence on Acid Strength and Isomer Distribution." ACS Catalysis 1(7):777-785.  doi:10.1021/cs2000939
  • Chen S, RJ Rousseau, S Raugei, M Dupuis, DL DuBois, and RM Bullock. 2011. "Comprehensive Thermodynamics of Nickel Hydride Bis(Diphosphine) Complexes: A Predictive Model through Computations." Organometallics 30(22):6108-6118.  doi:10.1021/om200645x
  • Dupuis M, S Chen, S Raugei, DL DuBois, and RM Bullock. 2011. "Comment on 'New Insights in the Electrocatalytic Proton Reduction and Hydrogen Oxidation by Bioinspired Catalysts: A DFT Investigation'." Journal of Physical Chemistry A 115(18):4861-4865.  doi:10.1021/jp111479z
  • Helm ML, MP Stewart, II, RM Bullock, M Rakowski DuBois, and DL DuBois. 2011. "A Synthetic Nickel Electrocatalyst With a Turnover Frequency Above 100,000 s-1 for H2 Production." Science 333(6044):863-866.  doi:10.1126/science.1205864
  • Kilgore UJ, JA Roberts, DH Pool, AM Appel, MP Stewart, II, M Rakowski DuBois, WG Dougherty, WS Kassel, RM Bullock, and DL DuBois. 2011. "[Ni(PPh2NC6H4X2)2]2+ Complexes as Electrocatalysts for H2 Production: Effect of Substituents, Acids, and Water on Catalytic Rates." Journal of the American Chemical Society 133(15):5861-5872.  doi:10.1021/ja109755f
  • Kilgore UJ, MP Stewart, II, ML Helm, WG Dougherty, WS Kassel, M Rakowski DuBois, DL DuBois, and RM Bullock. 2011. "Studies of a Series of [Ni(PR2NPh2)2(CH3CN)]2+ Complexes as Electrocatalysts for H2 Production: Substituent Variation at the Phosphorus Atom of the P2N2 Ligand." Inorganic Chemistry 50(21):10908-10918. 
  • Mock MT, S Chen, RJ Rousseau, MJ O'Hagan, WG Dougherty, WS Kassel, DL DuBois, and RM Bullock. 2011. "A Rare Terminal Dinitrogen Complex of Chromium." Chemical Communications 47(44):12212-12214.  doi:10.1039/C1CC15430C
  • O'Hagan MJ, WJ Shaw, S Raugei, S Chen, JY Yang, UJ Kilgore, DL DuBois, and RM Bullock. 2011. "Moving Protons with Pendant Amines: Proton Mobility in a Nickel Catalyst for Oxidation of Hydrogen." Journal of the American Chemical Society 133(36):14301-14312.  doi:10.1021/ja201838x
  • Roberts JA, DL DuBois, and RM Bullock. 2011. "Experimental and Digital Modeling Studies of the Electrochemical Oxidation of the Metal Anion [CpW(CO)2(IMes)]- and the 17-Electron Metal Radical CpW(CO)2(IMes)·. Kinetics and Thermodynamics of Capture and Release of MeCN by a Metal Radical and a Metal Cation." Organometallics 30(17):4555-4563.  doi:10.1021/om2002816
  • Roberts JA, AM Appel, DL DuBois, and RM Bullock. 2011. "Comprehensive Thermochemistry of W-H Bonding in the Metal Hydrides CpW(CO)2(IMes)H, [CpW(CO)2(IMes)H]·+, and [CpW(CO)2(IMes)(H)2]+. Influence of an N-Heterocyclic Carbene Ligand on Metal Hydride Bond Energies." Journal of the American Chemical Society 133(37):14604-14613.  doi:10.1021/ja202830w
  • Roberts JA, JA Franz, EF van der Eide, ED Walter, JL Petersen, DL DuBois, and RM Bullock. 2011. "Comproportionation of Cationic and Anionic Tungsten Complexes Having an N-Heterocyclic Carbene Ligand to Give the Isolable 17-Electron Tungsten Radical, CpW(CO)2(IMes)· ." Journal of the American Chemical Society 133(37):14593-14603.  doi:10.1021/ja202754e
  • Yang JY, RM Bullock, M Rakowski DuBois, and DL DuBois. 2011. "Fast and efficient molecular electrocatalysts for H2 production: Using hydrogenase enzymes as guides." MRS Bulletin 36(1):39-47.  doi:10.1557/mrs.2010.8

2010

  • Bullock RM. 2010. Catalysis Without Precious Metals, ed. R. Morris Bullock.  John Wiley & Sons, Inc., Hoboken, NJ. 
  • Bullock RM. 2010. "Molybdenum and Tungsten Catalysts for Hydrogenation, Hydrosilylation and Hydrolysis." Chapter 3 in Catalysis Without Precious Metals, ed. RM Bullock, pp. 51-81.  John Wiley & Sons, Inc., Hoboken, NJ. 
  • Chen S, S Raugei, RJ Rousseau, M Dupuis, and RM Bullock. 2010. "Homogeneous Ni catalysts for H2 Oxidation and Production: An Assessment of Theoretical Methods, from Density Functional Theory to Post Hartree-Fock Correlated Wave-Function Theory ." Journal of Physical Chemistry A 114(48):12716-12724.  doi:10.1021/jp106800n
  • Cheng TY, DJ Szalda, JA Franz, and RM Bullock. 2010. "Structural and Computational Studies of Cp(CO)2(PCy3)MoFBF3, a Complex with a Bound BF4- Ligand." Inorganica Chimica Acta 363(3):581-585.  doi:10.1016/j.ica.2009.02.028
  • Fagan PJ, MH Voges, and RM Bullock. 2010. "Catalytic Ionic Hydrogenation of Ketones by {[Cp*Ru(CO)2]2(? H)}+." Organometallics 29(4):1045-1048.  doi:10.1021/om901005k
  • Welch KD, WG Dougherty, WS Kassel, DL DuBois, and RM Bullock. 2010. "Synthesis, Structures, and Reactions of Manganese Complexes Containing Diphosphine Ligands With Pendant Amines." Organometallics 29(20):4532-4540.  doi:10.1021/om100668e
  • Wiedner ES, JY Yang, WG Dougherty, WS Kassel, RM Bullock, M Rakowski DuBois, and DL DuBois. 2010. "Comparison of Cobalt and Nickel Complexes with Sterically Demanding Cyclic Diphosphine Ligands: Electrocatalytic H2 Production by [Co(PtBu2NPh2)(CH3CN)3](BF4)2." Organometallics 29(21):5390-5401.  doi:10.1021/om100395r
  • Yang JY, RM Bullock, WG Dougherty, WS Kassel, B Twamley, DL DuBois, and M Rakowski DuBois. 2010. "Reduction of Oxygen Catalyzed by Nickel Diphosphine Complexes with Positioned Pendant Amines." Dalton Transactions 39(12):3001-3010. 
  • Yang JY, S Chen, WG Dougherty, WS Kassel, RM Bullock, DL DuBois, S Raugei, RJ Rousseau, M Dupuis, and M Rakowski DuBois. 2010. "Hydrogen Oxidation Catalysis by a Nickel Diphosphine Complex with Pendant tert-Butyl Amines." Chemical Communications 46:8618-8620.  doi:10.1039/C0CC03246H

2009

  • Ghosh P, PJ Fagan, WJ Marshall, E Hauptman, and RM Bullock. 2009. "Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol ." Inorganic Chemistry 48(14):6490-6500.  doi:10.1021/ic900413y
  • Schlaf M, P Ghosh, PJ Fagan, E Hauptman, and RM Bullock. 2009. "Catalytic Deoxygenation of 1,2-Propanediol to Give n-Propanol ." Advanced Synthesis & Catalysis 351(5):789-800. 
  • Yang JY, RM Bullock, WJ Shaw, B Twamley, K Fraze, M Rakowski DuBois, and DL DuBois. 2009. "Mechanistic Insights into Catalytic H2 Oxidation by Ni Complexes Containing a Diphosphine Ligand with a Positioned Amine Base." Journal of the American Chemical Society 131(16):5935-5945. 

2008

  • Cheng TY, DJ Szalda, JC Hanson, JT Muckerman, and RM Bullock. 2008. "Four-Electron Donor Hemilabile n3-PPh3 Ligand that Binds Through a C = C Bond Rather than an Agostic C-H Interaction, and Displacement of the C = C by Methyl Iodide or Water." Organometallics 27(15):3785-3795.  doi:10.1021/om800401d
  • Jacobsen GM, JY Yang, B Twamley, A Wilson, RM Bullock, M Rakowski DuBois, and DL DuBois. 2008. "Hydrogen Production Using Cobalt-Based Molecular Catalysts Containing a Proton Relay in the Second Coordination Sphere." Energy & Environmental Science 1(1):167-174.  doi:10.1039/b805309j

2007

  • Bullock RM. 2007. "An Iron Catalyst for Ketone Hydrogenations Under Mild Conditions ." Angewandte Chemie International Edition 46(39):7360-7363.  doi:10.1002/anie.200703053
  • Egbert JD, RM Bullock, and DM Heinekey. 2007. "Cationic Dihydrogen/Dihydride Complexes of Osmium: Structure and Dynamics." Organometallics 26(9):2291-2295.  doi:10.1021/om0700718
  • Wu F, VK Dioumaev, DJ Szalda, J Hanson, and RM Bullock. 2007. "A Tungsten Complex with a Bidentate, Hemilabile N-Heterocyclic Carbene Ligand, Facile Displacement of the Weakly Bound W-(C=C) Bond, and the Vulnerability of the NHC Ligand Toward Catalyst Deactivation During Ketone Hydrogenation." Organometallics 26(20):5079-5090.  doi:10.1021/om700694e

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