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

Abstract

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

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.

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

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