Redox Interconversion of Non-Oxido Vanadium Complexes Accompanied by Acid-Base Chemistry of Thiol and Thiolate

Jyun An Yan, Yu Sen Chen, Ya Ho Chang, Cheng Yun Tsai, Chiao Ling Lyu, Chun Gang Luo, Gene Hsiang Lee, Hua-Fen Hsu

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The redox nature of the non-oxido vanadium sulfur center is associated with several biological systems such as vanadium nitrogenase, the reduction of vanadium ion in ascidians, and the function of amavadin, which is a vanadium(IV) natural product contained in Amanita mushrooms. But the related chemistry is less explored and understood compared to oxido vanadium species due to the oxophilic character of high valent vanadium ions. Herein, we present a class of non-oxido vanadium thiolate complexes, [V III (PS2″S H ) 2 ] - (1) (PS2″S H = [P(C 6 H 3 -3-Me 3 Si-2-S) 2 (C 6 H 3 -3-Me 3 Si-2-SH)] 2- ), [V IV (PS3″)(PS2″S H )] - (2) (PS3″ = [P(C 6 H 3 -3-Me 3 Si-2-S) 3 ] 3- ), [V(PS3″) 2 ] - (3), [V(PS3″)(PS2″S H )] (4), and [V IV (PS3∗) 2 ] 2- (5a) (PS3∗ = [P(C 6 H 3 -3-Ph-2-S) 3 ] 3- ), and study their interconversion through the redox and acid-base reactions. Complex 1 consists of a six-coordinate octahedral vanadium center; complexes 2 and 4 are seven-coordinate with distorted capped trigonal prismatic geometry. Vanadium centers of 3 and 5a are both eight-coordinate; the former adopts ideal dodecahedral geometry, but the latter is better viewed as a distorted square antiprism. Complex 1 is oxidized to complex 2 and then to complex 3 with dioxygen. Each one-electron oxidation process is accompanied by the deprotonation of unbound thiol to bound thiolate. Complex 3 is also produced from complex 2 through stepwise addition of Fe(Cp) 2 + /n-BuLi, or in the reverse order. The formation of 2 from 3 is achieved in the order of adding Co(Cp) 2 and acid or, as with the previous complex, inversely. Notably, the reduction of complex 2 to complex 1 accompanying the protonation of bound thiolate to unbound thiol only occurs with the presence of both Co(Cp) 2 and acid, indicating a cooperative effect between the metal-centered reduction and bound thiolate protonation. The conversions among these complexes are observed with ESI-MS and UV-vis-NIR spectroscopies. The work demonstrates two-electron redox interconversion in these complexes mediated by transformations between unbound thiol and bound thiolate.

Original languageEnglish
Pages (from-to)9055-9063
Number of pages9
JournalInorganic Chemistry
Volume56
Issue number15
DOIs
Publication statusPublished - 2017 Aug 7

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Vanadium
Sulfhydryl Compounds
thiols
vanadium
chemistry
acids
Acids
Protonation
Oxidation-Reduction
Ions
Nitrogenase
Deprotonation
Geometry
Electrons
Biological systems
Biological Products
Sulfur
geometry
Metals
ions

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Yan, Jyun An ; Chen, Yu Sen ; Chang, Ya Ho ; Tsai, Cheng Yun ; Lyu, Chiao Ling ; Luo, Chun Gang ; Lee, Gene Hsiang ; Hsu, Hua-Fen. / Redox Interconversion of Non-Oxido Vanadium Complexes Accompanied by Acid-Base Chemistry of Thiol and Thiolate. In: Inorganic Chemistry. 2017 ; Vol. 56, No. 15. pp. 9055-9063.
@article{8a10406d53424deaa615b12ce8a0f15d,
title = "Redox Interconversion of Non-Oxido Vanadium Complexes Accompanied by Acid-Base Chemistry of Thiol and Thiolate",
abstract = "The redox nature of the non-oxido vanadium sulfur center is associated with several biological systems such as vanadium nitrogenase, the reduction of vanadium ion in ascidians, and the function of amavadin, which is a vanadium(IV) natural product contained in Amanita mushrooms. But the related chemistry is less explored and understood compared to oxido vanadium species due to the oxophilic character of high valent vanadium ions. Herein, we present a class of non-oxido vanadium thiolate complexes, [V III (PS2″S H ) 2 ] - (1) (PS2″S H = [P(C 6 H 3 -3-Me 3 Si-2-S) 2 (C 6 H 3 -3-Me 3 Si-2-SH)] 2- ), [V IV (PS3″)(PS2″S H )] - (2) (PS3″ = [P(C 6 H 3 -3-Me 3 Si-2-S) 3 ] 3- ), [V(PS3″) 2 ] - (3), [V(PS3″)(PS2″S H )] (4), and [V IV (PS3∗) 2 ] 2- (5a) (PS3∗ = [P(C 6 H 3 -3-Ph-2-S) 3 ] 3- ), and study their interconversion through the redox and acid-base reactions. Complex 1 consists of a six-coordinate octahedral vanadium center; complexes 2 and 4 are seven-coordinate with distorted capped trigonal prismatic geometry. Vanadium centers of 3 and 5a are both eight-coordinate; the former adopts ideal dodecahedral geometry, but the latter is better viewed as a distorted square antiprism. Complex 1 is oxidized to complex 2 and then to complex 3 with dioxygen. Each one-electron oxidation process is accompanied by the deprotonation of unbound thiol to bound thiolate. Complex 3 is also produced from complex 2 through stepwise addition of Fe(Cp) 2 + /n-BuLi, or in the reverse order. The formation of 2 from 3 is achieved in the order of adding Co(Cp) 2 and acid or, as with the previous complex, inversely. Notably, the reduction of complex 2 to complex 1 accompanying the protonation of bound thiolate to unbound thiol only occurs with the presence of both Co(Cp) 2 and acid, indicating a cooperative effect between the metal-centered reduction and bound thiolate protonation. The conversions among these complexes are observed with ESI-MS and UV-vis-NIR spectroscopies. The work demonstrates two-electron redox interconversion in these complexes mediated by transformations between unbound thiol and bound thiolate.",
author = "Yan, {Jyun An} and Chen, {Yu Sen} and Chang, {Ya Ho} and Tsai, {Cheng Yun} and Lyu, {Chiao Ling} and Luo, {Chun Gang} and Lee, {Gene Hsiang} and Hua-Fen Hsu",
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month = "8",
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Redox Interconversion of Non-Oxido Vanadium Complexes Accompanied by Acid-Base Chemistry of Thiol and Thiolate. / Yan, Jyun An; Chen, Yu Sen; Chang, Ya Ho; Tsai, Cheng Yun; Lyu, Chiao Ling; Luo, Chun Gang; Lee, Gene Hsiang; Hsu, Hua-Fen.

In: Inorganic Chemistry, Vol. 56, No. 15, 07.08.2017, p. 9055-9063.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Redox Interconversion of Non-Oxido Vanadium Complexes Accompanied by Acid-Base Chemistry of Thiol and Thiolate

AU - Yan, Jyun An

AU - Chen, Yu Sen

AU - Chang, Ya Ho

AU - Tsai, Cheng Yun

AU - Lyu, Chiao Ling

AU - Luo, Chun Gang

AU - Lee, Gene Hsiang

AU - Hsu, Hua-Fen

PY - 2017/8/7

Y1 - 2017/8/7

N2 - The redox nature of the non-oxido vanadium sulfur center is associated with several biological systems such as vanadium nitrogenase, the reduction of vanadium ion in ascidians, and the function of amavadin, which is a vanadium(IV) natural product contained in Amanita mushrooms. But the related chemistry is less explored and understood compared to oxido vanadium species due to the oxophilic character of high valent vanadium ions. Herein, we present a class of non-oxido vanadium thiolate complexes, [V III (PS2″S H ) 2 ] - (1) (PS2″S H = [P(C 6 H 3 -3-Me 3 Si-2-S) 2 (C 6 H 3 -3-Me 3 Si-2-SH)] 2- ), [V IV (PS3″)(PS2″S H )] - (2) (PS3″ = [P(C 6 H 3 -3-Me 3 Si-2-S) 3 ] 3- ), [V(PS3″) 2 ] - (3), [V(PS3″)(PS2″S H )] (4), and [V IV (PS3∗) 2 ] 2- (5a) (PS3∗ = [P(C 6 H 3 -3-Ph-2-S) 3 ] 3- ), and study their interconversion through the redox and acid-base reactions. Complex 1 consists of a six-coordinate octahedral vanadium center; complexes 2 and 4 are seven-coordinate with distorted capped trigonal prismatic geometry. Vanadium centers of 3 and 5a are both eight-coordinate; the former adopts ideal dodecahedral geometry, but the latter is better viewed as a distorted square antiprism. Complex 1 is oxidized to complex 2 and then to complex 3 with dioxygen. Each one-electron oxidation process is accompanied by the deprotonation of unbound thiol to bound thiolate. Complex 3 is also produced from complex 2 through stepwise addition of Fe(Cp) 2 + /n-BuLi, or in the reverse order. The formation of 2 from 3 is achieved in the order of adding Co(Cp) 2 and acid or, as with the previous complex, inversely. Notably, the reduction of complex 2 to complex 1 accompanying the protonation of bound thiolate to unbound thiol only occurs with the presence of both Co(Cp) 2 and acid, indicating a cooperative effect between the metal-centered reduction and bound thiolate protonation. The conversions among these complexes are observed with ESI-MS and UV-vis-NIR spectroscopies. The work demonstrates two-electron redox interconversion in these complexes mediated by transformations between unbound thiol and bound thiolate.

AB - The redox nature of the non-oxido vanadium sulfur center is associated with several biological systems such as vanadium nitrogenase, the reduction of vanadium ion in ascidians, and the function of amavadin, which is a vanadium(IV) natural product contained in Amanita mushrooms. But the related chemistry is less explored and understood compared to oxido vanadium species due to the oxophilic character of high valent vanadium ions. Herein, we present a class of non-oxido vanadium thiolate complexes, [V III (PS2″S H ) 2 ] - (1) (PS2″S H = [P(C 6 H 3 -3-Me 3 Si-2-S) 2 (C 6 H 3 -3-Me 3 Si-2-SH)] 2- ), [V IV (PS3″)(PS2″S H )] - (2) (PS3″ = [P(C 6 H 3 -3-Me 3 Si-2-S) 3 ] 3- ), [V(PS3″) 2 ] - (3), [V(PS3″)(PS2″S H )] (4), and [V IV (PS3∗) 2 ] 2- (5a) (PS3∗ = [P(C 6 H 3 -3-Ph-2-S) 3 ] 3- ), and study their interconversion through the redox and acid-base reactions. Complex 1 consists of a six-coordinate octahedral vanadium center; complexes 2 and 4 are seven-coordinate with distorted capped trigonal prismatic geometry. Vanadium centers of 3 and 5a are both eight-coordinate; the former adopts ideal dodecahedral geometry, but the latter is better viewed as a distorted square antiprism. Complex 1 is oxidized to complex 2 and then to complex 3 with dioxygen. Each one-electron oxidation process is accompanied by the deprotonation of unbound thiol to bound thiolate. Complex 3 is also produced from complex 2 through stepwise addition of Fe(Cp) 2 + /n-BuLi, or in the reverse order. The formation of 2 from 3 is achieved in the order of adding Co(Cp) 2 and acid or, as with the previous complex, inversely. Notably, the reduction of complex 2 to complex 1 accompanying the protonation of bound thiolate to unbound thiol only occurs with the presence of both Co(Cp) 2 and acid, indicating a cooperative effect between the metal-centered reduction and bound thiolate protonation. The conversions among these complexes are observed with ESI-MS and UV-vis-NIR spectroscopies. The work demonstrates two-electron redox interconversion in these complexes mediated by transformations between unbound thiol and bound thiolate.

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