Organometallic Chemistry of Carbon Dioxide: Organometallic Chemistry in Unusual Media

无机化学、生物无机化学和金属有机化学项目的这一奖项支持德克萨斯州农工大学化学系的唐纳德·J·达伦斯堡博士对二氧化碳的研究。这项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。收集到的信息将被用来为这些反应设计更具选择性的催化剂。钨、锌、镉和铜的络合物将被用来探索醇盐络合物的不稳定性，环氧化物与连接的羧酸盐的络合和取代偶联，以及催化剂的活性和选择性。此外，还将探索二氧化碳和氮杂环丙烷的金属催化共聚反应，以及二氧化碳与含有pi-给体配体的配位和电子不饱和金属羰基衍生物的反应性。两相催化和超临界二氧化碳将用于在这些均相过程中将催化剂从底物和产物中分离出来。二氧化碳是各种用途的潜在碳来源。此外，它还可以作为挥发性有机化合物的环境友好的替代溶剂。在这项研究中，催化剂将被设计用于二氧化碳作为合成有用聚合物的原料的反应。此外，超临界二氧化碳将作为溶剂进行测试，用于该过程中所需的一些分离。

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.