Characterization of the electronic structure of complexes containing metal-heteroatom multiple bonds.

Abstract

The electronic structure of a variety of metal-heteroatom multiply bonded complexes, including some active alkyne metathesis catalysts, have been investigated using He(I) and He(II) ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS) and Fenske-Hall molecular orbital calculations. Utilizing this electronic structure information, confirmation of the proposed mechanism for the alkyne metathesis reaction which involves formation of a metallacyclobutdienyl intermediate was ascertained. Also, the important relationships between metallatetrahedral and metallacyclobutadienyl complexes, both of which have been mentioned as possible intermediates in the alkyne metathesis reaction and for which examples have been prepared and isolated, are discussed in significant detail. In the final chapters the electronic structure of some corresponding metal-nitrogen triply bonded complexes are discussed as well as the results probing the charge distribution in metal-heteroatom multiply bonded systems as determined by the XPS experiment.