Theoretical Studies of Homogeneous Catalysis by Transition Metal Complexes

Citation

Rappé, Anthony Kay (1981) Theoretical Studies of Homogeneous Catalysis by Transition Metal Complexes. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/8kc4-gq42. https://resolver.caltech.edu/CaltechETD:etd-02032005-112022

Abstract

CHAPTER 1: Extensive ab initio calculations (double zeta plus polarization function basis with correlated wavefunctions) on the oxidation of hydrocarbons by chromyl chloride are combined with standard thermochemical methods to predict the energetics for oxidation of alkanes, alcohols, and alkenes. Additional results are presented on the analogous oxidations by molybdyl chloride. A common feature of all these reactions is identified and explained.

CHAPTER 2: Extensive ab initio calculations (double zeta plus polarization function basis with correlated wavefunctions) on the olefin metathesis reaction with high valent Mo and W catalysts are combined with standard thermochemical methods to predict the energetics of potential intermediates. The active catalyst is identified and explained together with several subsidiary features of the reaction manifold.

CHAPTER 3: A unifying generalized valence bond view of transition metal ligand bonding is presented as well as the energetics and structural characteristics of several ligand types. Additionally, the energetics for several ligand exchange reactions of potential synthetic utility are presented.

Thesis Files