Chemistry of Lewis Acidic Ligands: Hydrocarbon Functionalization, Borane "sigma-Complexes", and Catalytic Hydroboration

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This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports the research of Professor John F. Hartwig at Yale University. This work seeks to uncover unusual reactions and fundamental principles in the chemistry of metal-boryl and borane complexes by evaluating the chemistry of complexes with Lewis-acidic ligands. It endeavors to functionalize hydrocarbons with metal boryl complexes and to synthesize metallocene borane complexes related to catalytic hydroboration processes. These topics are to serve as case studies in how the electrophilicity of boryl ligands and borane substrates leads to new chemistry that has not been observed with more conventional organometallic systems. Boryl intermediates that interact with hydrocarbons will be investigated and substituent effects on selectivity will be measured in order to address how the electrophoricity of covalent ligands affects reactivity. Both fundamental and practical aspects of the early metal-borane and boryl species will be studied. The properties that stabilize or enhance the reactivity of these complexes will be studied with regard to their effects in catalytic hydroboration. The chiral selectivity of titanocene-catalyzed hydroboration and the selectivity of single addition to dienes will be studied.