Redox chemistry in the reaction of oxovanadium(V) with thiolate-containing ligands: The isolation and characterization of non-oxo vanadium(IV) complexes containing bisulfide and thioether groups

Hua Fen Hsu, Chia Ling Su, Neeruganti O. Gopal, Chi Chin Wu, Wei Cheng Chu, Yi Fang Tsai, Ya Ho Chang, Yi Hung Liu, Ting Shen Kuo, Shyue Chu Ke

Research output: Contribution to journalArticle

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Abstract

The reactions of VVO(O-iPr)3 with [PSS′]H 3 and [PS3]H3 |[PS3′]H3 = P(C 6H3-5-Me-2-SH)3, [PSS]H3 = P(C 6H4-2-SH)3} led to the formation of [V IV(L)] [L = P2S4′ (1a), P2S4 (1b)], where L was formed by the oxidative coupling of two PS3′ or PS3 ligands by a disulfide bond. When the reaction of VVO(O-iPr)3 with [PS3′]H3 was conducted in the presence of methoxide followed by the addition of a cation, [VIV(PS3′)-(PS2SMe′)]X [X = N(C 2H5)4 (2a), N(C2H5) 3(CH2Ph) (2b)] was isolated, where PS2S Me′ is a bis(benzenethiolato)phenylmethylthioetherphosphane ligand generated from the methylation of one thiolate group in PS3′. The structures of complexes 1a,b and 2a,b, determined by X-ray crystallography, contain six- and seven-coordinate non-oxo vanadium(IV) centers, respectively, with an octahedral geometry for 1a,b and a pentagonal-bipyramidal geometry for 2a,b. The electronic, magnetic, and electrochemical properties of these complexes were determined by UV/Vis and EPR spectroscopy, SQUID measurements, and cyclic voltammetry.

Original languageEnglish
Pages (from-to)1161-1167
Number of pages7
JournalEuropean Journal of Inorganic Chemistry
Issue number6
DOIs
Publication statusPublished - 2006 Mar 20

Fingerprint

Vanadium
Sulfides
Ligands
Methylation
Geometry
X ray crystallography
SQUIDs
Electrochemical properties
Disulfides
Electronic properties
Cyclic voltammetry
Paramagnetic resonance
Cations
Magnetic properties
Spectroscopy
Oxidation-Reduction

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Hsu, Hua Fen ; Su, Chia Ling ; Gopal, Neeruganti O. ; Wu, Chi Chin ; Chu, Wei Cheng ; Tsai, Yi Fang ; Chang, Ya Ho ; Liu, Yi Hung ; Kuo, Ting Shen ; Ke, Shyue Chu. / Redox chemistry in the reaction of oxovanadium(V) with thiolate-containing ligands : The isolation and characterization of non-oxo vanadium(IV) complexes containing bisulfide and thioether groups. In: European Journal of Inorganic Chemistry. 2006 ; No. 6. pp. 1161-1167.
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abstract = "The reactions of VVO(O-iPr)3 with [PSS′]H 3 and [PS3]H3 |[PS3′]H3 = P(C 6H3-5-Me-2-SH)3, [PSS]H3 = P(C 6H4-2-SH)3} led to the formation of [V IV(L)] [L = P2S4′ (1a), P2S4 (1b)], where L was formed by the oxidative coupling of two PS3′ or PS3 ligands by a disulfide bond. When the reaction of VVO(O-iPr)3 with [PS3′]H3 was conducted in the presence of methoxide followed by the addition of a cation, [VIV(PS3′)-(PS2SMe′)]X [X = N(C 2H5)4 (2a), N(C2H5) 3(CH2Ph) (2b)] was isolated, where PS2S Me′ is a bis(benzenethiolato)phenylmethylthioetherphosphane ligand generated from the methylation of one thiolate group in PS3′. The structures of complexes 1a,b and 2a,b, determined by X-ray crystallography, contain six- and seven-coordinate non-oxo vanadium(IV) centers, respectively, with an octahedral geometry for 1a,b and a pentagonal-bipyramidal geometry for 2a,b. The electronic, magnetic, and electrochemical properties of these complexes were determined by UV/Vis and EPR spectroscopy, SQUID measurements, and cyclic voltammetry.",
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Redox chemistry in the reaction of oxovanadium(V) with thiolate-containing ligands : The isolation and characterization of non-oxo vanadium(IV) complexes containing bisulfide and thioether groups. / Hsu, Hua Fen; Su, Chia Ling; Gopal, Neeruganti O.; Wu, Chi Chin; Chu, Wei Cheng; Tsai, Yi Fang; Chang, Ya Ho; Liu, Yi Hung; Kuo, Ting Shen; Ke, Shyue Chu.

In: European Journal of Inorganic Chemistry, No. 6, 20.03.2006, p. 1161-1167.

Research output: Contribution to journalArticle

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T1 - Redox chemistry in the reaction of oxovanadium(V) with thiolate-containing ligands

T2 - The isolation and characterization of non-oxo vanadium(IV) complexes containing bisulfide and thioether groups

AU - Hsu, Hua Fen

AU - Su, Chia Ling

AU - Gopal, Neeruganti O.

AU - Wu, Chi Chin

AU - Chu, Wei Cheng

AU - Tsai, Yi Fang

AU - Chang, Ya Ho

AU - Liu, Yi Hung

AU - Kuo, Ting Shen

AU - Ke, Shyue Chu

PY - 2006/3/20

Y1 - 2006/3/20

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AB - The reactions of VVO(O-iPr)3 with [PSS′]H 3 and [PS3]H3 |[PS3′]H3 = P(C 6H3-5-Me-2-SH)3, [PSS]H3 = P(C 6H4-2-SH)3} led to the formation of [V IV(L)] [L = P2S4′ (1a), P2S4 (1b)], where L was formed by the oxidative coupling of two PS3′ or PS3 ligands by a disulfide bond. When the reaction of VVO(O-iPr)3 with [PS3′]H3 was conducted in the presence of methoxide followed by the addition of a cation, [VIV(PS3′)-(PS2SMe′)]X [X = N(C 2H5)4 (2a), N(C2H5) 3(CH2Ph) (2b)] was isolated, where PS2S Me′ is a bis(benzenethiolato)phenylmethylthioetherphosphane ligand generated from the methylation of one thiolate group in PS3′. The structures of complexes 1a,b and 2a,b, determined by X-ray crystallography, contain six- and seven-coordinate non-oxo vanadium(IV) centers, respectively, with an octahedral geometry for 1a,b and a pentagonal-bipyramidal geometry for 2a,b. The electronic, magnetic, and electrochemical properties of these complexes were determined by UV/Vis and EPR spectroscopy, SQUID measurements, and cyclic voltammetry.

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