Organometallic Chemistry of Metallo Macrocycles

这个项目的重点是有机金属化合物，其中金属钴、铑或铱被结合到大环配体上，即有机分子提供几个给体原子来结合金属，其结构包含几个环。这种化合物在一氧化碳的还原偶联中显示出相当大的前景，在这个过程中一氧化碳被转化为更复杂和有用的有机分子。一系列达到可测量平衡的有机金属反应将用于推导热力学参数，以便随后用于估计M-H和M-C键能。通过溶剂效应、沸石包封和路易斯酸和碱的加入来改变反应环境，将被用作改变反应热力学和动力学的手段，以促进新的有机金属反应活性。铑和铱卟啉具有非常广泛的有机金属反应活性，包括C-H键活化、烯烃配位和氧化、杂双金属配合物的形成、一氧化碳的还原偶联以及与金属结合的碳、甲酰基或羟甲基的形成。一个主要的努力将是发现非卟啉大环和螯合配体系统，它们模拟金属卟啉的反应活性，但具有改进的反应速率特征。

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.