研究领域

Organometallic and Inorganic Chemistry

Research in the Heinekey group is focused on various aspects of transition metal organometallic chemistry. Major areas of investigation include synthetic, structural and mechanistic problems. A wide variety of analytical methods are employed in these investigations, with an emphasis on multinuclear NMR and x-ray crystallography. Professor Heinekey is also a member of the NSF-funded Center for Enabling New Technologies in Catalysis (CENTC), which draws together a group of investigators conducting research aimed toward the development of new catalytic systems. The study of transition metal hydride complexes is an area of broad interest to organometallic chemists. The practical impetus for this work stems from the importance of such complexes in many catalytic processes used by the chemical industry. A great variety of structural types and reactivity patterns are exhibited by metal hydride complexes, and complete elucidation of the structure and dynamics of these fascinating molecules is a challenging problem. Recent developments from this laboratory include the discovery of a very unusual quantum mechanical proton-proton coupling mechanism in a series of iridium complexes. The elucidation of this previously unknown coupling mechanism has caused a large body of literature on the dynamic behavior of metal polyhydrides to be targeted for reinvestigation in the light of these new findings. The existence of this process was established through the use of tritium NMR. This work is opening up several new possible applications of tritium NMR to a number of problems in organometallic chemistry. In related work, the interaction of the dihydrogen molecule with a variety of transition metal complexes is under active investigation. In some cases, stable complexes of intact bound dihydrogen have been isolated. The binding of hydrogen to transition metal Lewis acid centers has been found to dramatically alter the reactivity of hydrogen with respect to heterolytic cleavage. In some cases, hydrogen can become a very strong acid upon binding to the metal center. The isolation of these complexes affords an opportunity to study in detail the mechanism of activation of hydrogen by metal complexes, which is a reaction of fundamental importance in several catalytic processes, including the hydrogenase enzymes.

近期论文

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"Synthesis, Characterization and Reactivity of Iridium NHC Pincer Complexes" Katherine M. Schultz, Karen I. Goldberg, Dmitry G. Gusev and D. Michael Heinekey." Organometallics, 2011, 30, 1429. "Synthesis, Characterization and Reactivity of Arene-Stabilized Rhodium Complexes" Abby R. O’Connor, Werner Kaminsky, D. Michael Heinekey, and Karen I. Goldberg. Organometallics, 2011, 30, 2105. "Metal-free Carbon Dioxide Reduction and Acidic C-H Activations using a Frustrated Lewis Pair" Sophia D. Tran, Tristan A. Tronic, Werner Kaminsky, D. M. Heinekey and J. M. Mayer. Inorganica Chimica Acta, 2011, 369, 126. "Preparation of a Dihydrogen Complex of Cobalt" Travis J. Hebden, Anthony J. St. John, Dmitry G. Gusev, Werner Kaminsky, Karen I. Goldberg, D. Michael Heinekey. Angew. Chem. Int. Ed., 2011, 50, 1873. "A Carbonyl-rich Bridging Hydride Complex Relevant to the Fe-Fe Hydrogenase Active Site" Steve Matthews and D. M. Heinekey. Inorganic Chemistry,2010, 49, 9746. "Activation of Molecular Hydrogen" G. J. Kubas and D. M. Heinekey. Invited review chapter for Physical Inorganic Chemistry: Reactions, Processes and Applications. John Wiley & Sons, 2010. "Dihydrogen Complexes of the Chromium Group: Synthesis and Characterization of (Arene)M(CO)2(H2) Complexes ." Jonathan D. Egbert and D. M. Heinekey. Organometallics, 2010, 29, 3387. "Dihydrogen/Dihydride or Tetrahydride? An Experimental and Computational Investigation of Pincer Iridium Polyhydrides" Travis J. Hebden, Karen I. Goldberg, Alan S. Goldman, K. Krogh-Jespersen, Thomas J. Emge and D. M. Heinekey, Inorganic Chemistry, 2010, 49, 1733. "Dinuclear Iridium Complexes Containing Cp* and Carbonyl Ligands: Synthesis, Structure and Reactivity" Joseph Meredith, Karen I. Goldberg, Werner Kaminsky and D. M. Heinekey, Organometallics, 2009, 28, 3456. "Hydrogenase Enzymes: Recent Structural Studies and Active Site Models." D. M. Heinekey J. Organomet. Chem. 2009, 694,2671. "Activation of H2 by Palladium (0): Formation of the Monomeric Dihydride Complex trans [(IPr)(PCy3)Pd(H)2]" Serena Fantasia, Jonathan D. Egbert, Heiko Jacobsen, Luigi Cavallo, D. M. Heinekey and Steven P. Nolan. Angew. Chem. Int. Ed., 2009, 48, 5182. "Synthesis and Characterization of Sulfur Rich Iron(II) Carbonyl Dimers: Facile Reversible Reaction with Carbon Monoxide" Inigo Aguirre De Carcer and D. M. Heinekey J. Organomet. Chemistry, 2009, 694, 840. "Synthesis and Structure of Molybdenum and Tungsten Bisphosphine Carbonyl Dimers." Daniel F. Brayton and D. M. Heinekey. Organometallics, 2008, 27, 3901. "Iridium Catalyzed Dehydrogenation of Substituted Amine-Boranes: Kinetics, Thermodynamics and Implications for Hydrogen Storage." Brandon L. Dietrich, Karen I. Goldberg, D. M. Heinekey, Tom Autrey, John Linehan Inorg. Chem, 2008, 47, 8583. "Sigma Borane Complexes of Iridium: Synthesis and Structural Characterization." Melanie Denny, Travis J. Hebden, Vincent Pons, K. I. Goldberg, Paula Picolli, Arthur J. Schultz, Tom Koetzle and D. M. Heinekey, J. Am. Chem. Soc., 2008, 130, 10812. "C-H Bond Activation by Rhodium(I) Phenoxide and Acetate Complexes: Mechanism of H-D Exchange Between Arenes and Water" Susan M. Kloek, D. M. Heinekey and K. I. Goldberg. Organometallics, 2008, 27, 1454.