Structure-Reactivity Relations of Transition Metal ElectrodeReactions Characterized by Large Structural Change

本项目由无机、生物无机和有机金属化学项目资助，主要研究过渡金属配合物的非均相电子转移反应中的结构-反应性关系，重点研究伴随电子转移而发生较大内球结构变化的配合物。这项工作的主要目的是为结构和环境对异质电子转移速率的影响的现有理论提供定量测试。这将涉及测量非均相电子转移率的精确速率，并使用计算方法（分子力学和半经验和从头算量子力学）来模拟电子转移的内球势垒。第二个目标是开发提供精确的非均相速率常数的方法。电子转移是最基本的化学过程之一，我们对它了解很多，但仍有许多问题没有解决。这个项目是实验电化学家和理论物理化学家之间的合作成果，旨在提高我们对伴随电子转移的某些金属配合物结构变化如何影响整个过程速率的理解。

This project, supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program, involves studies of structure-reactivity relationships in heterogeneous electron transfer reactions of transition metal complexes with particular emphasis on complexes that undergo large inner sphere structural changes concommitant with the electron transfer. The primary objective of the work is to provide quantitative tests of current theories of structural and environmental effects on hetereogeneous electron transfer rates. This will involve the measurement of accurate rates of heterogeneous electron transfer rates and the use of computational methods (molecular mechanics and both semiempirical and ab initio quantum mechanistic) to model the inner sphere barrier to the electron transfer. A secondary objective is to develop methods that provide accurate heterogeneous rate constants. %%% Electron transfer is one of the most fundamental of chemical processes about which much is known but where many issues are unresolved. This project, which is a collaborative effort between an experimental electrochemist and a theoretical physical chemist, is designed to improve our understanding of how changes in the structures of certain metal complexes that accompany an electron transfer affect the rate of the overall process.