非血红素铁(III)活化氧分子反应的自旋轨道耦合和零场分裂

doi:10.3866/PKU.WHXB201306041

物理化学学报 >> 2013, Vol. 29 >> Issue (08): 1673-1680.doi: 10.3866/PKU.WHXB201306041

非血红素铁(III)活化氧分子反应的自旋轨道耦合和零场分裂

吕玲玲¹, 王小芳¹, 朱元成¹, 刘新文¹, 袁焜¹, 王永成²

1 天水师范学院生命科学与化学学院, 甘肃天水 741001;
2 西北师范大学化学化工学院, 兰州 730070

收稿日期:2013-02-27 修回日期:2013-06-03 发布日期:2013-07-09
通讯作者: 吕玲玲 E-mail:lvling100@163.com
基金资助:
国家自然科学基金(21263022)和甘肃省财政厅高校科研项目基金资助

Spin-Orbit Coupling and Zero-Field Splitting in Dioxygen Activation by Non-Heme Iron(III)

LV Ling-Ling¹, WANG Xiao-Fang¹, ZHU Yuan-Cheng¹, LIU Xin-Wen¹, YUAN Kun¹, WANG Yong-Cheng²

1 College of Life science and Chemistry, Tianshui Normal University, Tianshui 741001, Gansu Province, P. R. China;
2 College of Chemistry and Chemical Engineering, Northwest Normal University, LanZhou 730070, P. R. China

Received:2013-02-27 Revised:2013-06-03 Published:2013-07-09
Contact: LV Ling-Ling E-mail:lvling100@163.com
Supported by:
The project was supported by the National Natural Science Foundation of China (21263022) and University Research Fund of Gansu Province Financial Department, China.

摘要/Abstract

摘要：

采用密度泛函理论对原儿茶酚3,4-双加氧酶(3,4-PCD)活化O₂分子的反应机理进行了探讨. 初始复合物, 六重态⁶1的超快形成主要归因于电子交换诱导系间穿越(EISC), Fe d_z:O₂ π^*(z)是主要的交换通道, 在Fe―O键长为0.2487 nm处, 交换重叠积分S_ij=ád_z α|π^*(z) β>=0.3758. 从六重态⁶1 形成四重态中间体⁴1, 有两种效应共存, 即电子交换耦合作用和自旋轨道耦合(SOC)作用, 且相互竞争. 计算结果表明, 自旋轨道耦合(SOC)作用起主导因素(SOC=353.16 cm^-1). 至于O―O键的解离主要取决于儿茶酚(PCA)最高占据分子轨道(HOMO)的电子转移, 非血红素酶的铁中心仅承担PCA向O₂电子转移的缓冲作用.²²

关键词: 原儿茶酚3,4-双加氧酶, 自旋轨道耦合, 零场分裂, 反应机理

Abstract:

The mechanism of the O₂ activation by the protocatechuate 3,4-dioxygenase was investigated using density functional calculations. In the initial complex, the ultrafast formation of the sextet ⁶1 was probably the result of electron-exchange-induced intersystem crossing, and Fe d_z:O₂ π^*(z) was the dominant exchange pathway, with an overlap of d_z: O₂π^*(z) was dominant exchange pathway with the overlap of S_ij=ád_z α|π^*(z) β>=0.3758 at an Fe―O bond length of 0.2487 nm. Two coexisting effects, electron spin exchange coupling and spin-orbit coupling (SOC) in the sextet ⁶1, are responsible for formation of the quartet state ⁴1 from the sextet ⁶1. The exchange interaction competes with the SOC interaction as a driving force for spin conversion. The calculated results show that the latter is the dominant factor, because of the larger SOC constant (353.16 cm^-1). In cleavage of the O― O bond, electron transfer from the protocatechuate (PCA) highest occupied molecular orbital (HOMO) plays a vital role. The Fe center of the non-heme enzyme is a buffer to transfer an electron pair from the PCA HOMO to O₂.²²²

Key words: Protocatechuate 3,4-dioxygenase, Spin-orbit coupling, Zero-field splitting, Reaction mechanism

吕玲玲, 王小芳, 朱元成, 刘新文, 袁焜, 王永成. 非血红素铁(III)活化氧分子反应的自旋轨道耦合和零场分裂[J]. 物理化学学报, 2013, 29(08), 1673-1680. doi: 10.3866/PKU.WHXB201306041

LV Ling-Ling, WANG Xiao-Fang, ZHU Yuan-Cheng, LIU Xin-Wen, YUAN Kun, WANG Yong-Cheng. Spin-Orbit Coupling and Zero-Field Splitting in Dioxygen Activation by Non-Heme Iron(III)[J]. Acta Phys. -Chim. Sin. 2013, 29(08), 1673-1680. doi: 10.3866/PKU.WHXB201306041

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201306041

https://www.whxb.pku.edu.cn/CN/Y2013/V29/I08/1673

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非血红素铁(III)活化氧分子反应的自旋轨道耦合和零场分裂

Spin-Orbit Coupling and Zero-Field Splitting in Dioxygen Activation by Non-Heme Iron(III)

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