Single Crystal Reactions of Metal Carboxylates

利用结构文献作为固态反应设计的预测数据库，生成了一系列含有垂坠乙炔基团的活性金属羧酸盐。这些材料热反应，或在紫外线或y射线照射下，形成取代聚乙炔的金属配合物。这一努力的成功表明了类似的一系列金属羧酸盐的合成含有垂乙烯基。这些配合物立体特异反应形成二羧酸和三羧酸的结晶金属盐。结构信息确定了控制金属-乙炔配合物反应性的因素。然而，由于缺乏足够的乙烯基化合物结构信息，阻碍了这些相的结构-反应性关系的发展。对于这两个系列，提出了一套广泛的合成，机械和x射线结构实验，以便更好地了解导致各种加成反应的化学和结构因素。对同构相的研究有望加深我们对中心金属原子在这些固态反应中的作用的理解。除了用于合成之外，晶体反应物还具有作为指示物和剂量计的潜在应用。

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.