Michael Heinekey, Department of Chemistry, University of Washington is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program for explorations of metal-dihydrogen and metal-alkane interactions. Specifically, the project will target: (1) The structure and dynamics of elongated dihydrogen complexes using NMR spectroscopy and H/D/T labels; (2) Exchange coupling in symmetrical cis dihydrides using magnetic inequivalence to measure couplings; (3) Coordination of sigma bonds such as C-H and Si-H bonds to electrophilic metal centers generated by photoextrusion of CO or by chloride abstraction using silyl cation reagents; (3) Low barrier dynamics, including the measurement of kinetic isotope effects, of cis H2 /H systems using very low temperature NMR spectroscopy and isotope substitution; (3) Intramolecular activation of the strong C-H bonds in pyrazolyl rings by intermolecular activation and possible functionalization of hydrocarbon C-H bonds using neutral and/or cationic Ir(I) complexes
An important current goal of research in homogeneous catalysis is to understand the metal binding and activation of substrates such as dihydrogen, alkanes and silanes which present only sigma bonds for interaction with the metal center Information about these species has previously been available only through indirect measures, but in this study they will be directly observed. In addition, the education and training of future scientists and the development of new NMR methods are major impacts of this work.
