Homogeneous Catalytic Carbonylation of Nitroaromatics and Related Studies

在化学部无机、生物无机和有机金属计划的这一项目中，格拉菲尔特将研究某些催化剂如何促进硝基芳香化合物转化为异氰酸酯。该项目的一个可能结果是，为异氰酸酯的生产提供了一种更安全、更环保的方法，异氰酸酯是一种重要的商业化学品。将试图阐明硝基芳烃均相催化羰化反应的机理，该反应可能能够取代目前以光气为基础的异氰酸酯生产技术。这些方法包括催化的动力学研究，高温高压下的原位FTIR和核磁共振光谱，以及催化中间体的分离和表征。将研究三种Ru羰基催化剂：含有双(二苯基膦)甲烷配体的单体，最近发现的含有两个双(二甲基膦)甲烷配体的双核物种，以及三Ru十二烷基。

In this project in the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division, Gladfelter will study how certain catalysts promote the conversion of nitroaromatic compounds into isocyanates. A possible outcome of the project is a safer and more environmentally benign method for the production of isocyanates, an important class of commercial chemicals. Attempts will be made to elucidate the mechanism of the homogeneous catalytic carbonylation of nitroaromatics, a reaction that may be capable of replacing the current phosgene- based technology for the production of isocyanates. The methods involve kinetic studies of the catalysis, in situ FTIR and NMR spectroscopies conducted at high temperature and pressure, and isolation and characterization of catalytic intermediates. Three ruthenium carbonyl catalysts will be studied: a monomer containing the bis(diphenylphosphino)methane ligand, the recently discovered binuclear species containing two bis(dimethylphosphino)methane ligands, and triruthenium dodecacarbonyl.