Organometallic Charge Transfer and the Reduction of Carbon Dioxide

这个无机、生物无机和有机金属项目的奖项支持普渡大学化学系的Clifford Kubiak博士在减少二氧化碳方面的工作。含有三个镍原子和桥接二（二苯基膦）甲烷桥接基团的有机金属簇化合物已被发现可作为将二氧化碳加成烯烃的光催化剂和将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系统将使用基质中的低温光化学、激光瞬态吸收方法的动力学、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电子耦合的作用，并将制备配体键长和电子性质系统变化的新团簇组件。本文主要研究了二氧化碳与过渡金属配合物的反应。将采用化学、光化学和电化学手段来促进二氧化碳的还原，包括将来自该源的碳与其他碳原子结合以形成更长的碳链的反应。这些研究涉及到如何利用从大气供过于求中获得的二氧化碳的问题。

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.