Date of Award

Summer 2000

Degree Type

Thesis - Restricted

Degree Name

Master of Science (MS)

Department

Chemistry

Abstract

Nucleophilic attack on coordinated polyenes is one of the paradigms of 7torganometallic chemistry. Where reactions of this type occur with predictable regioselectivity they can be of synthetic utility. Reactions of iron cations and other transition-metal cations with nucleophiles have been studied extensively. Rhodium complexes are often used as catalysts in various organic syntheses. Novel rhodium complexes have been synthesized and characterized, as well as the isomerization reactions of the co-ordinated diene complexes. Protonation of cyclopentadienyl rhodium (I) complexes with olefins has been studied in some detail. Less work bas been reported on nucleophilic addition to rhodium cations. The nucleophilic addition to (cyclohexadienyl)(cyclopentadienyl) Rhodium cation has been tested in this thesis work, reasonable yields have been obtained. In cyanide attack, the isomerization from 1 ,4-diene to 1 ,3-diene has been observed, and a mechanism has been proposed to account for this observation. As a complement to the experimental study of cyclopentadienyl rhodium complexes, the B3LYP density functional method (DFT) has been applied using Gaussian 98. This investigation has provided detailed structural and energetical information, which generates a deeper understanding of those complexes. The mechanism of the isomerization reaction has been examined carefully in both gas phase and in solution.

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