Polymerization methods for the synthesis of photosensitive organometallic polymers with molybdenum-molybdenum bonds in the backbone.

This dissertation outlines the synthesis and characterization of novel dimeric organometallic complexes that are used to generate polymers with metal-metal bonds in the main-chain. These polymers are photo-reactive and are used extensively in the mechanistic study of photochemical polymer degradation. Despite their utility, the synthesis of polymers with metal-metal bonds in the backbone is a virtually unexplored area in the field of macromolecular chemistry.-Chapter I chronicles the motivation for studying polymers with metal-metal bonds in the backbone, the synthetic methods employed in the preparation of organometallic complexes with reactive metal-metal bonds, and the various polymerization methods explored for the preparation of these polymers. Chapter II describes the synthetic method for preparing a new complex, [(eta 5C5H5)Mo(CO)2(Ph2P(CH 2)6CH=CH2)]2, and attempts topolymerize it using Acyclic Diene Metathesis (ADMET). The complex did not form a polymer as expected and control experiments evaluating its polymerizability are also described. Chapter III details the synthesis, ADMET polymerization, and characterization of the cis-Mo(CO)4(Ph2P(CH2) 3CH=CH2)2 complex. Although this polymer does not contain metal-metal bonds it is one of the few reported examples of a transition-metal-containing polymer prepared by ADMET.-Chapter IV details the synthesis, characterization, and ADMET polymerization of the [(eta5-C5H4(CH2) 8CH=CH2)Mo(CO)3]2 complex. The activity of this complex in ring-closing metathesis reactions and in photochemical reactions with CCl4 is also reported. Finally, in chapter V the synthesis and characterization of the [(eta5-C5H 4(CH2)3OCO(CH2)3C≡CH)Mo(CO) 3]2 complex are described. The reactivity of this complex in coupling reactions using the copper-catalyzed Huisgen cycloaddition reaction is also discussed. Chapter VI provides a summary of this research.-This dissertation includes previously published and unpublished co-authored material.