The Electron Rich Triple Bond and Associated Multi-Electron Redox Chemistry

本项目隶属于无机、生物无机和有机金属化学专业，主要研究含金属-金属三键化合物的反应化学。我们将研究最近发现的八卤二盐酸盐（III）阴离子的结构和反应，以期(a)确定决定阴离子内旋转几何形状的空间和电子因素，以及(b)使用这些化合物作为合成各种单核和双核锇化合物的起始材料。​将开发合成策略，以制备含有桥接硫和砷配体的三键的二氮配合物。三键的dihencore经受4电子氧化的能力将被用于将磷化氢卤化dihenium配合物转化为多氢化dihenium，以及烷基和芳基腈还原偶联得到金属-亚胺配合物。这些反应应该构成这类化合物的重要合成策略。具有铼-铼三键的铼（II）配合物与六核三角棱柱状铼（II）团簇化合物之间的关系将通过尝试合成和结构表征后者来检验。含有金属-金属键的化合物作为催化剂和合金的前体继续引起人们的兴趣。

This project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is concerned with the reaction chemistry of compounds containing metal-metal triple bonds. The structures and reactions of salts of the recently discovered octahalodiosmate(III) anions will be examined with a view to (a) establishing the steric and electronic factors that determine the rotational geometry within the anions and (b) using these compounds as starting materials for the synthesis of various mononuclear and dinuclear osmium compounds. Synthetic strategies will be developed for the preparation of triply-bonded dirhenium(II) complexes which contain bridging sulfur and arsenic ligands. The ability of the triply-bonded dirhenium core to undergo a 4-electron oxidation will be utilized in the conversion of dirhenium phosphine halide complexes into dirhenium polyhydrides and in the reductive coupling of alkyl and aryl nitriles to give metal-imido complexes. These reactions should constitute important synthetic strategies to such classes of compounds. The relationship between dirhenium(II) complexes with rhenium-rhenium triple bonds and hexanuclear trigonal prismatic rhenium(II) cluster compounds will be examined through attempts to synthesize and structurally characterize the latter. Compounds containing metal-metal bonds continue to be of interest as catalysts and as precursors for alloys.