Organometallic Charge Transfer and the Reduction of Carbon Dioxide

普渡大学化学系克利福德·库比亚克博士是 由无机，生物无机和有机物计划支持， 化学部的电荷转移的调查， 有机金属系统，发生在振动时间尺度上， 可以在马库斯-库什理论的框架内进行解释， 电子转移价间电荷转移发生在 振动时间尺度在一些triruthenium集群，作为证据， 羰基红外伸缩带的合并，以及 这些络合物中的电子交换速率反映了 复合物内的电子耦合。在这个项目中， 控制这种耦合的控制器将被描绘。一个自洽的物理 对这一现象的描述将通过详细的 三钌的动态红外平均光谱研究 配合物然后，通过对以下问题的研究， 三个额外的强耦合有机金属电荷转移 配合物：（i）三核透明镍的横向互连二聚体 簇;（ii）具有强金属-金属的低聚金属簇 相互作用;和（iii）新的四（二苯基膦基）醌二甲烷 桥联双核金属配合物。这些复合体中的许多具有 合适的氧化还原电位和催化性能， 二氧化碳的电化学还原，以及它们的这一方面 化学将被开发。 电子在反应物和产物之间的转移是一个关键的过程。 在许多化学反应中。在这些过程中， 电子转移由溶剂内的振动速率定义 关于反应物和产物分子的运动。这项研究涉及 电子转移过程发生在相同的速度， 分子的振动，并将决定因素，控制 电子转移速率结果将允许更好的基本 了解电子转移，并为设计系统提供基础 具有调谐的电子转移特性。基本的应用 在项目中获得的知识将通过设计系统来展示 能够化学活化二氧化碳。

Dr. Clifford P. Kubiak, Department of Chemistry, Purdue University, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for an investigation of charge transfer in organometallic systems that occur on the vibrational time scale and that can be interpreted within the framework of the Marcus-Hush theories of electron transfer. Intervalence charge transfer occurs near the vibrational time scale in some triruthenium clusters, as evidenced by coalescence of carbonyl infrared stretching bands, and differences in the electron exchange rates in these complexes reflect differences in the electronic coupling within the complexes. In this project the factors that control this coupling will be delineated. A self consistent physical description of the phenomenon will be developed through detailed spectroscopic studies of the dynamical IR averaging in the triruthenium complexes. The picture then will be generalized by investigations of three additional, strongly coupled organometallic charge transfer complexes: (i) laterally interconnected dimers of trinuclear clear nickel clusters; (ii) oligomeric metal clusters with strong metal-metal interactions; and (iii) new tetra(diphenylphosphino) quinodimethane bridged dinuclear metal complexes. Many of these complexes have appropriate redox potentials and catalytic properties for the electrochemical reduction of carbon dioxide, and this aspect of their chemistry will be developed. The transfer of electrons between reactants and products is a critical step in many chemical reactions. In these processes the maximum rate of electron transfer is defined by the rate of vibrations within and solvent motions about the reactant and product molecules. This study addresses electron transfer processes that take place at the same speed as molecular vibrations and will determine the factors that control the electron transfer rate. The results will permit both a better basic understanding of electron transfer and provide a basis to design systems with tuned electron transfer properties. The application of the basic knowledge gained in the project will be demonstrated by devising systems that are capable of chemically activating carbon dioxide.