Understanding Metal-Catalyzed High Pressure Carbonylations of Organic Compounds

明尼苏达大学化学系的Wayne L. Gladfelter博士将研究金属催化有机化合物羰基化的机理。这个环境友好的化学合成和加工项目将由无机、生物无机和有机金属化学项目提供支持。Gladfelter将与Catalytica的John Grate博士合作。原位红外和核磁共振方法将用于监测硝基芳烃羰基化反应形成异氰酸酯。催化剂前驱体将是Ru3(CO)12和具有膦和亚磷酸盐配体的各种钌羰基。这项工作与环境良性合成的相关性在于，这些反应提供了一种绕过在合成异氰酸酯时使用光气（一种有害的中间体）的方法。进一步的研究将集中在这些催化剂和相关催化剂在极性化合物的不对称合成和氢化中的应用。聚氨酯在化学工业中大量生产，特别是在绝缘材料的生产中。目前的聚氨酯路线需要将硝基芳香族转化为异氰酸酯化合物，在此转化过程中大量使用剧毒物质光气。研究一种不需要光气的新型催化方法。目前，该方法显示出很大的前景，但它的工作原理还需要进一步了解。Catalytica是一家总部位于加州的公司，为石油炼制、能源和化学工业创造并商业化经济和环境有利的催化技术。

Dr. Wayne L. Gladfelter of the Chemistry Department, University of Minnesota, will investigate the mechanisms of metal-catalyzed carbonylations of organic compounds. Support for this Environmentally Benign Chemical Synthesis and Processing project will be provided by the Inorganic, Bioinorganic, and Organometallic Chemistry program. Gladfelter will collaborate with Dr. John Grate of Catalytica. In situ IR and NMR methods will be used to monitor carbonylation reactions of nitroaromatics to form isocyanates. The catalyst precursors will be Ru3(CO)12 and various ruthenium carbonyls having phosphine and phosphite ligands. The pertinence of the work to Environmentally Benign Synthesis is that the reactions afford a method to bypass the use of phosgene (a hazardous intermediate) in the synthesis of isocyanates. Additional studies will focus on the use of these and related catalysts in asymmetric synthesis and hydrogenation of polar compounds. %%% Polyurethanes are produced in great quantity in the chemical industry, especially in the production of insulation. The present route to polyurethanes entails the conversion of nitroaromatic to isocyanate compounds with a highly toxic species, phosgene, being used in great amounts during this conversion. A new catalytic method that bypasses the use of phosgene is to be studied. At present the method shows great promise, but much needs to be learned about how it functions. Catalytica is a California-based company that creates and commercializes economic and environmentally advantageous catalytic technologies for the petroleum refining, energy, and chemical industries.