Staff information

Biography

Morris Bullock is the Director of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center. He is a Laboratory Fellow in the the Catalysis Sciences Group in the Chemical and Materials 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

• Member of the Editorial Advisory Board (2005-2007) for the American Chemical Society journal Inorganic Chemistry, and a member of the Editorial Advisory Board (2000-2002) for the American Chemical Society journal Organometallics.
• Chairman of the Gordon Conference on Organometallic Chemistry in 2003. Organizer of two symposia at American Chemical Society meetings.
• Received the Science and Technology Award in 2002 from Brookhaven Science Associates.

PNNL Publications

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