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

这项奖助金提供五年总统青年研究员奖第一年的基本经费。该研究属于有机金属化学领域，主要研究金属原子与周围配体之间含有多个键的化合物的光诱导反应。这项研究将包括两个项目。首先，将研究含有多个金属配体键的高价有机金属配合物的光化学反应。特别令人感兴趣的是配合物的光化学反应，其中金属有两个d电子，要么与氮配体三键结合，要么与烷基炔或烷基烯配体双键结合。这些物质的最低电子激发态，即相对于多键配体的pi-反键，应该促进这些部分的反应。第二个项目将涉及杂双金属化合物的合成和物理表征，其中金属中心由无机底物连接。重点将放在电子不饱和的早期过渡金属配合物与含有可作为早期过渡金属桥梁的配体的晚期金属化合物的反应上。具体来说，16电子氢化物配合物与二氮、一氧化碳或二氧化碳连接的电子饱和配合物的反应应该产生以这些配体为桥的二聚体。

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.