Ketene Complexes: Structure, Bonding, Catalysis, and Interconversion with Carbene Complexes

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Dr. Douglas B. Grotjahn, Chemistry Department, San Diego State University, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division for research into the chemistry of metal ketene complexes. Metal-ketene complexes are important intermediates in unique bond-forming reactions starting from carbene complexes and they allow rapid access to a variety of organic products, many of which would require multistep syntheses using standard organic reactions. However, nearly all of these processes are stoichiometric in the metal complex. The goal of the project is to develop catalytic reactions that are likely to become attractive synthetic organic procedures. To achieve this, new ketene complexes will be prepared and catalytic systems developed from them. Specifically, unusually stable Ir and Rh ketene complexes will be prepared, metal-ketene bonding within them will be characterized by X-ray diffraction and IR and NMR spectroscopy, the thermodynamic and kinetic relationships between(C,C)and (C,O) linkage isomers will be delineated, and the interconversion of carbene-CO and ketene complexes will be studied. Using these data, catalytic carbon-carbon bond-forming reactions involving ketene or carbene complexes as intermediates will be developed.The proposed research will contribute to the fields of organometallic and organic chemistry and catalysis, relevant to both organic synthesis and industrial chemistry. Ultimately, more convenient, less-toxic large scale synthetic preparations of organic compounds will be possible. In addition to the basic science, underrepresented minority and undergraduate students will be trained during the course of the project.