Comparison Between [FeⅣ(O)(TMC)(NCMe)]2+ and [FeⅣ(O)(TMCS)]+ Non-heme Complexes of Geometric, Electronic Structures, Bonding and Reactivities

Chem. J. Chinese Universities

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Comparison Between [FeⅣ(O)(TMC)(NCMe)]2+ and [FeⅣ(O)(TMCS)]+ Non-heme Complexes of Geometric, Electronic Structures, Bonding and Reactivities

WANG Yi, WANG Yong, HAN Ke-Li*

State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

Received:2008-10-13 Revised:1900-01-01 Online:2008-12-10 Published:2008-12-10
Contact: HAN Ke-Li

Abstract

Abstract: Density functional theory(DFT) calculations were carried out to elucidate the electronic structures, Fe—O bondings and reactivities of six-coordinated [FeⅣ(O)(TMC)(NCMe)]2+ and [FeⅣ(O)(TMCS)]+ complexes. The geometric parameters calculated by a hybrid functional UB3LYP with LanL2DZ(Fe) and TZV(rest) basis set were in agreement with the experimental data. Analysis of the orbital coefficients and the bond orders showed that the TMC ligand does not have any equivalent orbitals that are affecting the Fe—O π bond. Due to the strong mixing of the iron 3d orbitals with the σ orbital of the thiolate ligand orbitals and a much less mixing with the acetonitrile as an axial ligand, the electronic properties of [FeⅣ(O)(TMC)(NCMe)]2+ and [FeⅣ(O)(TMCS)]+ are different and the Fe—O bond length of the [FeⅣ(O)(TMCS)]+ complex is longer than that of the [FeⅣ(O)(TMC)(NCMe)]2+ complex.

Key words: Non-heme, Orbital coefficient, Electronic structure, Density functional theory calculation

CLC Number:

O641

TrendMD:

WANG Yi, WANG Yong, HAN Ke-Li*. Comparison Between [FeⅣ(O)(TMC)(NCMe)]2+ and [FeⅣ(O)(TMCS)]+ Non-heme Complexes of Geometric, Electronic Structures, Bonding and Reactivities[J]. Chem. J. Chinese Universities, doi: .

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Comparison Between [FeⅣ(O)(TMC)(NCMe)]2+ and [FeⅣ(O)(TMCS)]+ Non-heme Complexes of Geometric, Electronic Structures, Bonding and Reactivities

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