Organometallic Chemistry and Photochemistry of Supported and Unsupported Metal-Metal Bonds

含有两个金属原子与一个金属原子直接键合的化合物 另一个是目前非常感兴趣的，因为他们 催化性能，也因为它们的效用， 出现在异质表面的物种模型 催化剂的许多这些金属-金属键合的化合物是 高度着色，因此易受光影响 诱导反应，因此它们有可能用作 光化学或光电化学催化剂 应用. 本项目的重点是化学和光化学 金属-金属键合的有机-过渡金属络合物。两 类的配合物将被研究：i）那些包含 未被支撑的M-M σ键，和ii）含有M-M σ键的那些 由桥连CO、CNR或二膦配体支撑的键。 基于激发态的有机金属化学将得到发展 单桥d-10-d-10双核配合物的态 配体（CO、CNR或NO+）。激发态在 将桥连配体活化为双分子烷基化，或 将确定缩合反应。正式的<$2 +2！ 烯烃、乙炔和 将探索具有桥连配体的累积多烯。新 类桥连配体环加成反应的<$4 +2！ 和<$2 +2+2！类型也将得到发展。<$4 +2}加法 的二烯桥CO和CNR配体和<$2 +2+2！ 烯烃与一对桥连CO和CNR的缩合反应 将检查配体。二氧化碳的新化学性质 开发，包括探索其环加成， 桥连CO和CNR配体，以及O-原子转移， 与草酸盐衍生物的还原偶联。

Compounds containing two metal atoms directly bonded to one another are of great current interest because of their catalytic properties and also because of their utility as models of species which occur at the surfaces of heterogeneous catalysts. Many of these metal-metal bonded compounds are highly colored and consequently are susceptible to light induced reactions, so that they have potential for use as catalysts for photochemical or photoelectrochemical applications. The focus of this project is the chemistry and photochemistry of metal-metal bonded organo-transition metal complexes. Two classes of complexes will be studied: i) those which contain unsupported M-M sigma bonds, and ii) those which contain M-M bonds supported by bridging CO, CNR or di-phosphine ligands. New organometallic chemistry will be developed based on excited states of d-10-d-10 binuclear complexes with a single bridging ligand (CO, CNR, or NO+). The roles of excited states in activating the bridging ligand toward bimolecular alkylation or condensation reactions will be determined. The formal ı2+2! photocycloaddition chemistry of olefins, acetylenes, and cumulenes with the bridging ligand will be explored. New classes of bridging ligand cycloaddition reactions of the ı4+2! and ı2+2+2! types will also be developed. The ı4+2} additions of dienes to bridging CO and CNR ligands and ı2+2+2! condensations of olefins with a pair of bridging CO and CNR ligands will be examined. New chemistry of carbon dioxide will be developed, including exploration of its cycloadditions to bridging CO and CNR ligands, as well as O-atom transfers and reductive couplings to oxalate derivatives.