氧原子转移试剂存在条件下金属羰基化合物的CO取代动力学研究

Kinetics and Mechanism of CO Substitution of Metal Carbonyls in the Presence of O atom Transfer Reagents

氧原子转移试剂存在下金属羰基化合物ＣＯ取代反应动力学的系统研究表明，反应速率对金属羰基化合物、氧原子转移试剂和进入试剂的浓度分别为一级、一级和零级。这表明反应可能为缔合机理，过程涉及转移试剂氧原子在羰碳原子上发生亲核进攻，生成一个良好离去基团ＣＯ２的同时产生了一个活性中间体，后者与进入试剂发生快反应得产物。从金属羰基化合物和氧原子转移试剂两个方面讨论了影响ＣＯ取代反应速率的各种因素。

Kinetic studies of CO substitution of metal carbonyls in the presence of O atom transfer reagents show the reaction rates are first order in metal carbonyl and in O atom transfer reagent concentrations, but zero order in entering ligand concentration. This suggests an associative mechanism where a carbonyl carbon atom is attacked by the O atom of the reagent, affording the good leaving group CO 2 and generating an active intermediate which readily reacts with the entering ligand to produce the substituted product. Various factors relating to the metal carbonyls and to the O atom transfer reagents that effect the rates of CO substitution are discussed.