过渡金属络合催化活性顺序的量子化学研究 Ⅰ对烯烃的活化

本文应用以HMO为主简化的量子化学方法研究过渡金属络合活化烯烃分子(以乙烯为例)的催化活性。结果表明过渡金属的催化活性与过渡金属本身的d电子组态和d轨道能级、络合分子的π成键轨道和π~*反键轨道的能级、配位体的电荷性质和空间构型等诸因素有密切的联系。这一结果基本上可以解释过渡金属催化活性顺序、助催化剂及配位体对催化活性的影响等实验规律。

A Quantum Chemical Investigation of Catalytic Activity Series of Transition Metals on Coordination Catalysis (I) Activation of Olefins

In this paper we have investiged the catalytic activies of transition metals for the activation of olefins by quantum chemical method. As a result, it has been found that the catalytic activity of a transition metal is closely related with the d-electron configuration and drorbital energy-level of the transition metal. It also depends upon the π-bonding molecular orbital energy-level and π*-antibonding molecular orbital energy-level of the coordinated molecule. In addition, it is related with electric charge properties and spatial structure of liqand. The result can basically explaine experimental law of catalytic activity series of transition metals as well as the law of effects of auxiliary catalyst and liqand on catalytic activity.