Single Crystal Reactions of Metal Carboxylates

这项工作的目的是对两种具有烯烃或乙炔基团的羧酸盐进行一套综合的合成、机械和x射线结构实验。固体反应可由辐照（紫外线、x射线、伽马射线）和/或加热引起。研究的重点是反应的物理和化学机理。这些实验将导致对固体反应的结构-反应性关系的理解的改进，以及在固体中立体特异性和区域特异性合成的有效规划和执行。为了提高对分子晶体辐射化学的认识，将在金属的吸收边缘附近用特定波长的同步加速器x射线照射金属配合物。固体合成化合物的明显优点包括效率或选择性的提高，以及以大大提高的收率制备传统溶液化学无法获得的化合物的能力。对不饱和羧酸盐的固态反应性进行了广泛的研究。广泛的一般反应性的发现，特别是金属盐的发现，有望开辟固态合成的新领域。从化学和物理两方面探讨了单晶反应的机理。获得的关于金属在不饱和羧酸盐反应中的作用的信息将增强对分子晶体辐射化学的理解。

The goal of this work is to conduct a comprehensive set of synthetic, mechanistic, and X-ray structural experiments on two types of carboxylate salts having alkene or acetylene groups. Solid-state reactions will be induced by irradiation (UV, X-rays, gamma rays) and/or by heating. The investigation will focus on the physical and chemical mechanism of the reactions. These experiments will lead to improvements in the understanding of structure-reactivity relationships for solid-state reactions, and in the effecient planning and execution of stereospecific and regiospecific syntheses in solids. To enhance the understanding of the radiation chemistry of molecular crystals, metal complexes will be irradiated by synchrotron x-radiation at specific wavelength near the absorption edge of the metal. %%% The distinct advantages of solid-state syntheses of chemical compounds include improvements in efficiency or selectivity, and the ability to prepare compounds unavailable by conventional solution chemistry at greatly improved yields. A broad investigation is proposed on the solid-state reactivity of salts of unsaturated carboxylic acids. The discovery of extensive general reactivity, particularly for metal salts, promises to open new areas of solid-state synthesis. The mechanism of single crystal reactions will be probed from both chemical and physical points of view. Information gained regarding the role of the metal in the reactions of unsaturated carboxylate will enhance the understanding of radiation chemistry of molecular crystals.