This project, in the Inorganic, Bioinorganic, and Organometallic Chemistry Program, deals with the mechanisms and synthetic applications of niobocene complexes of ketenes as oxygen transfer reagents to nitriles, isonitriles and ketones. The first two classes of substrates are converted to isocyanates (the conversion of the nitrile involves an alkyl group migration) and the latter to carboxylic acid esters, with regiochemistry that is opposite to that seen in traditional Baeyer-Villiger methods. In each case the organometallic product is a vinylidene complex. A major objective of the work is the development of a catalytic process for mild oxidation of the above substrates based on the niobocene vinylidene complex and readily available reagents as oxygen atom sources. Oxidation is one of the most important reactions in synthetic organic chemistry. New methods for selective oxidation are therefore important research targets. This project has as its primary objective the development of a new catalyst for the mild oxidation of several organic substrates. If successful, the method could have considerable potential in the synthesis of new biologically active compounds such as drugs, pesticides, herbicides, etc.
