Studies of Highly Reactive Molecules and Intermediates

The Organic Synthesis Program will support the continuation of the research of Dr. Paul G. Gassman. Dr. Gassman will continue his productive studies on highly strained systems and initiate work on the synthesis of ligands for transition metals. These will be used to change the apparent oxidation state of the metal. This increased control of the oxidation state will facilitate the synthesis of the increasingly complex materials needed by our economy. Studies in the area of organometallic chemistry will be centered on the use of X-ray photoelectron spectroscopy (XPS) to understand the electronic influence of ligands on complexed transition metals. New ligands will be prepared which are either more electron withdrawing or electron donating than currently available ligands. It is planned to prepare and study the properties of complexes which can serve as either oxidants or reductants as a function of the attached ligands. Work will continue on studies of trans-bicycloın.1.0!alkanes, strained paracyclophanes, and electron transfer from strained rings. New synthetic applications of electrochemical reductions will be explored. Improved excited state oxidants will be sought in an approach to the development of synthetically useful procedures for anti-Markovnikov addition of nucleophiles to simple olefins. Studies of radicals, anion radicals, cation radicals and cations will be carried out.