This grant from the Organic Dynamics Program supports the computational studies of Professor Bachrach at Northern Illinois University. The studies focus on (a) the pericyclic chemistry of thiones and thioaldehydes and (b) nucleophilic substitutions at phosphor and sulfur. The calculations will concentrate on the phospha- and thia-Claisen rearrangements, Diels-Alder reactions involving the CS double bond, the dimerization of thiaketenes, and the addition-elimination mechanism of the nucleophilic substitution at sulfur. Ab initio quantum mechanical methods at high theoretical levels will be employed to determine reaction energies, structures, and electron densities. In this computational project Dr. Bachrach will extend the theory of reaction mechanism from carbon to the heteroatoms phosphor and sulfur by an examination of pericyclic and nucleophilic substitutions. The various components of these fundamental studies will be valuable compliments to gas phase and solution work and thereby are of interest to a broad chemical audience.
