Presidential Young Investigator Award/Electronic Spectroscopy, Photochemistry, and Photophysics of High-Valent Organometallic Complexes

这笔赠款提供了第一年的基本资金， 五年总统青年调查员奖研究 是在有机金属化学领域，并侧重于 含多键化合物的光诱导反应 在金属原子和周围的配体之间。 该研究将包括两个项目。中的第一 这些高价有机金属的光化学反应 含有多个金属-配体键的络合物将是 研究了特别感兴趣的是光化学 金属有两个d电子的络合物的反应 并且与氮化物配体三键或双键结合 键合到亚烷基或亚烷基配体上。的 这些物质的最低电子激发态， 是相对于多键配体的π-反键， 应该促进这些部分的反应。第二 项目将涉及综合和物理 杂环化合物的表征，其中 金属中心通过无机基底连接。重点 将在电子不饱和的反应早期 过渡金属与后一种金属化合物的配合物 含有一个配体，可以作为桥梁， 过渡金属具体来说，16电子的反应 电子饱和配合物的氢化物配合物 通过二氮、一氧化碳或二氧化碳连接， 产生具有这些配体作为桥的二聚体。

This grant provides the base funding for the first year of a five-year Presidential Young Investigator award. The research is in the area of organometallic chemistry and focuses on light-induced reactions of compounds containing multiple bonds between the metal atom and one of the surrounding ligands. The research will consist of two projects. In the first of these, photochemical reactions of high-valent organometallic complexes containing multiple metal-ligand linkages will be investigated. Of particular interest are photochemical reactions of complexes in which the metal has two d electrons and is either triply bonded to a nitride ligand or doubly bonded to either an alkylidyne or an alkylidene ligand. The lowest-lying electronic excited states of these species, which are pi-antibonding with respect to the multiply bonded ligand, should facilitate reactions at these moieties. The second project will involve the synthesis and physical characterization of heterobimetallic compounds in which the metal centers are joined by an inorganic substrate. Emphasis will be on the reactions of electronically unsaturated early transition metal complexes with compounds of the later metals containing a ligand which can serve as a bridge to the early transition metal. Specifically, the reaction of 16-electron hydride complexes with electronically saturated complexes ligated by dinitrogen, carbon monoxide or carbon dioxide should yield dimers with these ligands as bridges.