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

该项目属于无机、生物无机和有机金属化学专业，涉及与有机反应催化有关的铂族化学的几个方面的研究。具体研究领域包括：1)进一步研究利用对氢诱导极化（PHIP）作为氢化反应反应机制的核磁共振探针；2)通过与阳离子和奇电子铑和铱的反应激活有机分子；3)铑和铱配合物在水中的反应，以及作为树突结构的一部分；前者对环境友好型技术有影响，而后者可能提供一种对底物进行辨别的手段，因此具有选择性。对于水溶液功，要使用的配体将使金属配合物具有水溶性。大多数工业生产过程都使用某种类型的催化剂，以提高反应速率，从而以更低的能源成本提高产量，并经常改变产品的选择性。新的催化剂和改进的催化过程既需要对可能的新催化剂进行探索性研究，也需要对现有催化剂有更好的机理理解。此外，如果在有机溶剂中运行的现有催化系统可以转换为水溶液过程，可能会产生更环保的过程。这个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.