Single Crystal Reactions of Metal Carboxylates

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Using the structural literature as a predictive database for the design of solid state reactions, a series of reactive metal carboxylates containing pendant acetylene groups was generated. These materials react thermally, or under UV- or y-irradiation, to form metal complexes of substituted polyacetylenes. The success of this effort suggested the synthesis of an analogous series of metal carboxylates containing pendant vinyl groups. Theses complexes react stereospecifically to form crystalline metal salts of di-and tricarboxylic acids. Structural information has defined the factors governing the reactivity of the metal-acetylene complexes. However, the lack of sufficient structural information on the vinyl compounds has prevented the development of structure-reactivity relationships for these phases. For both series an extensive set of synthetic, mechanistic, and x-ray structural experiments are proposed in order to gain a greater understanding of the chemical and structural factors which lead to various types of addition reactions. A proposed study of isomorphous phases promises to deepen our understanding of the role of the central metal atom in these solid state reactions. In addition to their use in synthesis, the crystalline reactants have potential applications as indicators and dosimeters.