FeTPP和CoTPP电化学氧化还原的量子化学研究

用限制性的CNDO/2方法研究了FeTPP和CoTPP不同还原阶段的电子结构,结果表明,在FeTPP还原反应中第一个还原电子和Fe的d轨道相作用,第二个还原电子与卟啉环的4个氮原子及同它相连的8个碳原子的p轨道相作用,而CoTPP的2个还原电子与Co的d轨道相互作用,这与紫外原位光谱的实验结果完全一致。

The Quantum Chemistry Studies on Electrochemical Oxidation-Reduction of FeTPP and CoTPP

The electronic structures of electrochemical reduction reaction in different steps for FeTPP and CoTPP have been studied by restricted CNDO/2 method. The results show that in the electrochemical reduction reaction of FeTPP the first electron interacts with d orbitals of the central Fe atom, whereas the second electron interacts with p orbitals of four nitrogen atoms, and eight carbon atoms connected with the four nitrogen atoms respectively. However, all the two electrons of CoTPP interact with d orbitals of the central Co atom separately. This is in good agreement with the results obtained in an in-situ UV spectroscopic experiment.