Organometallic Chemistry of Carbon Dioxide: Organometallic Chemistry in Unusual Media

这个无机、生物无机和有机金属化学项目的奖项支持德克萨斯农工大学化学系Donald J. Darensbourg博士对二氧化碳的研究。研究的主要重点是二氧化碳和环氧化物共聚形成聚碳酸酯的基本过程。收集到的信息将用于为这些反应设计更具选择性的催化剂。钨、锌、镉和铜配合物将用于探测醇氧配合物的稳定性、环氧化物络合和随后与连接羧酸盐的偶联，以及催化剂的活性和选择性。此外，还将探讨金属催化二氧化碳与叠氮吡啶共聚形成聚氨酯的反应，并研究二氧化碳与含有pi-供体配体的配位和电子不饱和金属羰基衍生物的反应性。在这些均相过程中，双相催化和超临界二氧化碳将用于催化剂与底物和产物的分离。二氧化碳是多种用途的潜在碳源。此外，它还可以作为一种环保的挥发性有机化合物的替代溶剂。在这项研究中，催化剂将被设计用于以二氧化碳为原料合成有用聚合物的反应。此外，超临界二氧化碳将作为该过程中某些分离所需的溶剂进行测试。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research on carbon dioxide by Dr. Donald J. Darensbourg of the Chemistry Department, Texas A&M University. The main focus of the research is on the fundamental processes occurring during copolymerization of carbon dioxide and epoxides to form polycarbonates. Information gleaned will be used to design more selective catalysts for those reactions. Tungsten, zinc, cadmium, and copper complexes will be used to probe the lability of alkoxide complexes, epoxide complexation and subseqent coupling with ligated carboxylates, and catalyst activity and selectivity. In addition, metal catalyzed copolymerization reactions of carbon dioxide and aziridines to form polyurethane will be explored, and reactivity of carbon dioxide with coordinatively and electronically unsaturated metal carbonyl derivatives that contain pi-donor ligands will be investigated. Biphasic catalysis and supercritical carbon dioxide will be used for catalyst separation from the substrate and the product in these homogeneous processes. Carbon dioxide is a potential source of carbon for various uses. Also, it can serve as an environmentally-benign replacement solvent for volatile organic compounds. In this study, catalysts will be designed for reactions in which carbon dioxide is used as a source material for synthesis of useful polymers. In addition, supercritical carbon dioxide will be tested as a solvent for some of the separations needed in the process.