New insight into the electronic structure of iron(IV)-oxo porphyrin compound I. A quantum chemical topological analysis

摘要: The electronic structure of iron-oxo porphyrin p-cation radical complex Por �þ Fe IV ¼ O( SAH) has been studied for doublet and quartet states by means two methods the quantum chemical topology analysis: electron localization function (ELF) g(r) density q(r). formation this leads to essential perturbation topological carbon‐carbon bonds in moiety. double C¼ ¼C pyrrole anion subunits, represented pair bonding disynaptic basins Vi¼1,2(C,C) isolated porphyrin, are replaced single attractor V(C,C)i¼1‐20 after complexation with cation. iron‐nitrogen covalent dative bonds, N!Fe, described V(Fe,N)i¼1‐4, where is almost formed lone pairs N atoms. nature iron‐ oxygen bond predicted ELF analysis, shows a main contribution electrostatic interaction, dþ ��� O d� ,a s long as no attractors between C(Fe) C(O) core were found, although there common surfaces iron basines coupling pairs, that could be interpreted charge-shift bond. FeAS bond, characterized basin V(Fe,S), partially donated from sulfur atom. change state (M 2) 4) reorganization spin polarization, which observed only skeleton (� 0.43e 0.50e) SAH 0.55e 0.52e). V C 2012 Wiley Periodicals, Inc.