An Eight-Coordinate Vanadium Thiolate Complex with Charge Delocalization between V(V)−Thiolate and V(IV)−Thiyl Radical Forms | Zendy

Ya-Ho Chang | Zendy; Chia-Ling Su | Zendy; RuRong Wu | Zendy; JuHsiou Liao | Zendy; YiHung Liu | Zendy; HuaFen Hsu | Zendy

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An Eight-Coordinate Vanadium Thiolate Complex with Charge Delocalization between V(V)−Thiolate and V(IV)−Thiyl Radical Forms

Author(s) -

Ya-Ho Chang,

Chia-Ling Su,

RuRong Wu,

JuHsiou Liao,

YiHung Liu,

HuaFen Hsu

Publication year - 2011

Publication title -

journal of the american chemical society

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 7.115

H-Index - 612

eISSN - 1520-5126

pISSN - 0002-7863

DOI - 10.1021/ja2004208

Subject(s) - chemistry , delocalized electron , vanadium , electron paramagnetic resonance , crystallography , charge (physics) , stereochemistry , computational chemistry , inorganic chemistry , nuclear magnetic resonance , organic chemistry , quantum mechanics , physics

A six-coordinate oxovanadium(V) thiolate complex and an eight-coordinate non-oxovanadium thiolate complex, [PPh(4)][VO(PS3'')(OCH(3))] (1) and [NEt(4)][V(PS3'')(2)] (2) (PS3'' = P(C(6)H(3)-3-Me(3)Si-2-S)(3)(3-)), respectively, have been isolated and structurally characterized. The former belongs to a limited collection of oxovanadium(V) thiolate complexes. The latter has an unusual coordination number of eight. More importantly, its consensus electronic structure derived from its spectroscopic data should be considered as the resonance forms of V(V)-thiolate and V(IV)-thiyl radical species. This implies that V(IV)-thiyl radical can maintain a stable presence in biological systems.

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