Organometallic Charge Transfer and the Reduction of Carbon Dioxide

无机、生物无机和有机金属项目的这一奖项支持普渡大学化学系的Clifford Kubiak博士减少二氧化碳的工作。含有三个镍原子和桥联双(二苯基膦)甲烷桥基的有机金属簇合物被发现是二氧化碳与烯烃加成反应的光催化剂，也是二氧化碳还原为草酸盐的电催化剂。这些以及新合成的光催化和电催化体系将使用基质中的低温光化学、激光瞬时吸收动力学方法、红外光谱电化学和快速扫描伏安法进行研究。该项目的另一个目标是阐明相互连接的金属团簇之间的电子耦合作用，并将制备具有系统变化的配体键长和电子性质的新的团簇组装体。本文主要研究了二氧化碳与过渡金属络合物的反应。将采用化学、光化学和电化学方法来促进二氧化碳的还原，包括将来自该来源的碳与其他碳原子键合形成更长的碳链的反应。这些研究涉及寻找二氧化碳的良好用途的问题，这些二氧化碳可能是从大气供应过剩中获得的。

This award in the Inorganic, Bioinorganic, and Organometallic Program supports the work of Dr. Clifford Kubiak of the Chemistry Department, Purdue University, on reduction of carbon dioxide. Organometallic cluster compounds containing three nickel atoms and bridging bis(diphenylphosphino)methane bridging groups have been found to act as photocatalysts for the addition of carbon dioxide to alkenes, and as electrocatalysts for the reduction of carbon dioxide to oxalate. These, as well as newly synthesized, photocatalytic and electrocatalytic systems will be investigated using low temperature photochemistry in matrices, kinetics by laser transient absorption methods, infrared spectroelectrochemistry, and rapid scan voltammetry. Another goal of the project is to elucidate the role of electronic coupling between interconnected metal clusters, and new cluster assemblies in which ligand bond length and electronic properties are systematically varied will be prepared. This research is focused on reactions of carbon dioxide with transition metal complexes. Chemical, photochemical, and electrochemical means will be employed to promote the reduction of carbon dioxide, including reactions in which carbon from this source is bonded to other carbon atoms to form longer carbon chains. These studies are relevant to the problem of finding good uses for carbon dioxide that might be obtained from an atmospheric oversupply.