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Type of Document	Dissertation
Author	Rappe, Anthony Kay
URN	etd-02032005-112022
Persistent URL	http://resolver.caltech.edu/CaltechETD:etd-02032005-112022
Title	Theoretical studies of homogeneous catalysis by transition metal complexes
Degree	PhD
Option	Chemistry
Advisory Committee	Advisor Name Title William A. Goddard Committee Chair
Keywords	None
Date of Defense	1980-10-20
Availability	restricted
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.
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