金属卟啉催化氧化烃类饱和C—H键的理论模拟研究进展

Advances in theoretical simulation of hydrocarbon saturated C—H bonds oxidation catalyzed by metalloporphyrin

金属卟啉作为仿生催化剂在催化氧化烃类饱和C—H键领域得到了非常广泛的应用,其高效的催化性能也成为实验和理论模拟研究中的焦点。由于理论模拟研究不受实验条件的限制,更适于研究反应的复杂机理,因此在金属卟啉催化氧化烃类饱和C—H键领域受到了广泛关注。本文系统地综述了近年来金属卟啉仿生催化剂催化氧化烃类饱和C—H键的理论模拟研究,重点介绍了几种常用的理论模拟方法以及金属卟啉几何和电子性质的理论计算,同时详细地论述了理论模拟方法用于金属卟啉活化氧气和催化氧化烃类饱和C—H键的机理研究,并展望了金属卟啉仿生催化剂的理论模拟发展方向,指出多种理论模拟方法有机结合用于研究金属卟啉催化氧化的机理及金属卟啉结构与催化选择性之间的关系将是今后的主要研究方向。

Metalloporphyrins have been widely used as biomimetic catalysts in the catalytic oxidation of saturated C—H bonds in hydrocarbon,and their efficient catalytic performance has become the focus of both experimental and theoretical researches.Since theoretical simulation is not limited by experimental conditions and is more suitable for studying the complex reaction mechanisms,it has attracted extensive attentions in the field of catalytic oxidation of saturated C—H bonds by metalloporphyrins.In this paper,the advance in the theoretical simulation of saturated C—H bond oxidation of hydrocarbons catalyzed by metalloporphyrin biomimetic catalysts in recent years is reviewed.Several commonly used theoretical simulation methods and their applications in the calculation of the geometric and electronic properties of metalloporphyrins are emphatically introduced.At the same time,the theoretical simulation studies on the mechanisms of activation of oxygen and catalytic oxidation of saturated C—H bonds of hydrocarbons by metalloporphyrins are discussed in detail.The development directions of theoretical simulation of metalloporphyrins biomimetic catalysts are prospected,which mainly include the organic combination of various simulation methods to study the catalytic mechanism and the relationship between the structure of metalloporphyrins and the catalytic selectivity.