Studies on the Chemistry of Platinum Group Element Complexes and Applications to Catalysis

在无机化学、生物无机化学和金属有机化学计划中，这个项目涉及到铂族化学的几个方面的研究，这些方面与有机反应的催化有关。有待进一步研究的具体领域包括：1)进一步研究使用对氢激发极化(PhIP)作为氢化反应中反应机理的核磁共振探针；2)通过与阳离子和奇电子的Rh和Ir物种反应激活有机分子；3)Rh和Ir络合物在水中的反应以及作为树枝状结构的一部分；前者对环境友好的技术有影响，而后者可提供底物区分和选择性的手段。对于水溶液的工作，将使用的配体将赋予金属络合物的水溶解性。大多数工业生产过程使用某种类型的催化剂，这有助于提高反应速度，从而以较低的能源成本增加产量，并经常改变产品的选择性。新的催化剂和改进的催化工艺既需要对可能的新催化剂进行探索性研究，也需要更好地了解现有催化剂的机理。此外，如果现有的在有机溶剂中运行的催化系统可以转换为水溶液工艺，则可能会产生更环保的工艺。该项目在这三个领域都有目标。

This project, in the Inorganic, Bioinorganic, and Organometallic Chemistry Program, involves the study of several aspects of platinum group chemistry as related to catalysis of organic reactions. Specific areas to be pursued include 1) further examination of the use of parahydrogen induced polarization (PHIP) as an NMR probe of reaction mechanisms in hydrogenation reactions, 2) activation of organic molecules by reaction with cationic and odd electron rhodium and iridium species, and 3) reactions of rhodium and iridium complexes in water and as part of dendrimeric structures; the former has implications for environmentally friendly technologies whereas the latter may provide a means of substrate discrimination and therefore selectivity. For the aqueous solution work, the ligands to be used will impart water solubility to the metal complexes. The majority of industrial manufacturing processes use some type of catalyst, which serves to increase reactions rates and, therefore, increase throughput with lower energy costs, and frequently to alter product selectivity. New catalysts and improved catalytic processes require both exploratory studies of possible new catalysts and the better mechanistic understanding of existing catalysts. In addition, more environmentally acceptable processes may result if existing catalytic systems that operate in organic solvents can be converted to aqueous solution processes. This project has objectives in all three of these areas.