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

这笔赠款为为期五年的总统青年调查员奖的第一年提供了基本资金。这项研究是在有机金属化学领域，重点是含有金属原子和周围配体之一之间的多个键的化合物的光诱导反应。这项研究将包括两个项目。在第一部分中，我们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金属有两个d电子的络合物的光化学反应，其中金属与氮化物配体三键或双键与亚烷基或亚烷基配体。这些物种的最低电子激发态相对于多键配体是pi-反键，应该有助于在这些部分进行反应。第二个项目将涉及异质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络合物与含有可作为通往早期过渡金属的桥梁的配体的后期金属化合物的反应上。具体地说，16电子氢化物络合物与氮、一氧化碳或二氧化碳连接的电子饱和络合物的反应应该产生以这些配体为桥梁的二聚体。

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.