Inner-Shell Structural Effects in Electron Transfer Reactions

印第安纳大学普渡大学的Franklin Schutz得到了无机、生物无机和有机金属化学项目的支持，他的研究旨在通过研究涉及精心挑选的过渡金属化合物家族的反应的电化学激活参数，了解内部配位壳结构变化对电子转移反应速率的影响。特别感兴趣的方面是：a)内壳层重排对电子转移驱动力的熵分量的贡献；B)自旋变化对电子转移速率的影响；C)配体桥接双核配合物中受内配位球结构影响的多电子转移。本课程所研究的反应类型在许多具有高度实际重要性的化学反应系统中至关重要，例如工业催化，生物呼吸，神经回路功能。虽然在过去的几十年里，在理解这些过程方面取得了很大的进展，但许多基本的问题仍然没有得到解答，部分原因是很难找出影响电子转移过程速率的许多微妙的化学影响。在这个程序中，高度复杂的电化学和化学技术将被用来分离和研究这些问题中最紧迫的几个。这一努力的成功有望在许多科学领域产生红利。

Franklin Schutz of Indiana University Purdue University at Indianapolis is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program for research designed to understnd the consequences of inner coordination-shell structural changes on rates of electron-transfer reactions, through study of electrochemical activation parameters for reactions involving carefully-selected families of transition metal compounds. Aspects that will be of particular interest are: a) contributions of inner-shell rearrangements to the entropic component of the driving force of electron transfer; b) the influence of spin-changes on rates of electron transfer; c) multielectron transfer in ligand-bridged binuclear complexes as influenced by structure of the inner coordination spheres involved.The class of reactions that are being studied in this program is of critical importance in many types chemical reaction systems that are of high practical importance -- industrial catalysis, biological respiration, functioning of neural circuits, for instance. Although great progress has been made in the past several decades in understanding these processes, many fundamental questions remain unanswered, in part because of the difficulty of sorting out the many subtle chemical influences that bear on the rates of electron-transfer processes. In this program, highly sophisticated electrochemical and chemical techniques will be used to isolate and investigate several of the most pressing of these questions. Success in this effort may be expected to yield dividends in many scientific areas.