Coordination Complexes with Multiple Inorganic Functional Groups

该奖项通过NSF化学合成计划资助，支持约翰F。威斯康星州-麦迪逊大学的Berry旨在利用多个无机官能团来促进多电子过程。在此，“无机官能团”被定义为能够进行至少一种氧化还原反应的单元。因此，组合多个官能团应导致观察到同一分子可进行的多个氧化还原反应。例如，具有Mo（II）-Mo（II）四重键“官能团”的化合物可以经历双电子氧化以产生三重键合的Mo（III）-Mo（III）物质，并且金属-氧代“官能团”可以经历双电子氧原子转移过程。这两个官能团可以以允许可逆的四电子氧化还原和O-原子转移反应发生的方式组合。在这项工作中，化合物的探索，联合收割机无机官能团将提供一个途径，走向发现新的多电子反应。无机官能团的研究范围从金属-金属多重键（包括金属氧代、卡宾和氮化物）到异金属物种（其中每个金属作为单独的官能团）。多电子反应在化学和生物过程中非常重要。例如，分子（如分子氧）的多电子还原不仅在生物学上很重要，发生在有氧呼吸中，而且在重要的能源相关技术中发挥关键作用，如燃料电池和水分解。化学界的一个根本挑战是提高这种多电子反应的效率。促进多电子化学的新方法具有重要意义，该奖项支持了旨在发现新的多电子反应的概念性进展。这一进展涉及将不同过渡金属化合物的特性结合起来，每个过渡金属化合物都能够进行电子转移，成为能够进行多电子转移的新化合物。

This award funded through the NSF Chemical Synthesis program supports work in the research group of John F. Berry at the University of Wisconsin--Madison aimed at using multiple inorganic functional groups to promote multi-electron processes. Here an "inorganic functional group" is defined as a unit capable of at least one redox reaction. Thus, combining multiple functional groups should lead to the observation of multiple redox reactions available to the same molecule. For example, a compound having a Mo(II)-Mo(II) quadruple bond 'functional group' can undergo two-electron oxidation to yield a triply-bonded Mo(III)-Mo(III) species, and a metal-oxo 'functional group' can undergo two-electron oxygen atom transfer processes. These two functional groups can be combined in such a way as to permit reversible four-electron redox and O-atom transfer reactions to take place. In this work, the exploration of compounds that combine inorganic functional groups will provide a pathway towards the discovery of new multi-electron reactions. The inorganic functional groups to be studied range from metal-metal multiple bonds, including metal oxo, carbene, and nitrido compounds, to heterometallic species in which each metal serves as a separate functional group.Multi-electron reactions are very important in chemistry as well as in biological processes. For example, multi-electron reductions of molecules such as molecular oxygen are not only biologically important, occurring in aerobic respiration, but also play key roles in important energy-related technologies, such as fuel cells and water splitting. A fundamental challenge in the chemical community is to improve the efficiency of such multi-electron reactions. New ways to facilitate multielectron chemistry are of great significance, and this award supports a conceptual advance aimed toward the discovery of new multi-electron reactions. This advance involves combining traits of different transition metal compounds, each individually capable of electron transfer, into new compounds able to perform multi-electron transfer.