Organometallic Chemistry of Metallo Macrocycles

该项目的重点是有机金属化合物，其中 金属钴、铑或铱与大环 配体，即提供几种供体的有机分子 用于结合金属的原子，并且其结构包含 几个戒指。这类化合物显示出相当大的应用前景 在一氧化碳的还原偶联中， 其中一氧化碳被转化为更复杂的， 有用的有机分子。 一系列有机金属反应， 平衡将用于推导热力学参数 用于随后估计M-H和M-C键能。 溶剂效应引起的反应环境的变化， 沸石包封和添加刘易斯酸和碱 将被用来改变反应 热力学和动力学，以促进新的 有机金属反应性铑铱卟啉 物种有一个非凡的宽度的有机金属 反应性，包括C-H键活化的区域， 烯烃配位和氧化，形成 杂环配合物，碳的还原偶联 一氧化物，以及与卡宾、甲酰基或 与金属结合的羟甲基物质。一项重大努力将 发现非卟啉大环和螯合物 模拟金属卟啉反应性的配体体系，但 其具有改进的反应速率特性。

The focus of this project are organometallic compounds in which the metals cobalt, rhodium or iridium are bound to macrocyclic ligands, i.e. organic molecules which provide several donor atoms for binding the metal and whose structures contain several rings. Such compounds show considerable promise for use in the reductive coupling of carbon monoxide, a process in which carbon monoxide is converted to more complicated and useful organic molecules. A series of organometallic reactions that achieve measurable equilibria will be used in deriving thermodynamic parameters for subsequent use in estimating M-H and M-C bond energies. Variation of the reaction environment by solvent effects, zeolite encapsulation and addition of Lewis acids and bases will be exploited as a means of altering reaction thermodynamics and kinetics in order to promote new organometallic reactivity. Rhodium and iridium porphyrin species have an extraordinary breadth of organometallic reactivity, which encompasses the areas of C-H bond activation, alkene coordination and oxidation, formation of heterobimetallic complexes, reductive coupling of carbon monoxide, and the formation of species with carbene, formyl or hydroxymethyl species bound to the metal. A major effort will be made to discover non-porphyrinic macrocycles and chelate ligand systems which emulate metalloporphyrin reactivity, but which have improved reaction rate characteristics.