The Ligand-based Reactivity of Vanadium-thiolate Complexes

• Main Authors: Tzu-TsoChen, 陳咨佐
• Other Authors: Hua-Fen Hsu
• Format: Others
• Language: en_US
• Published: 2010
• Online Access: http://ndltd.ncl.edu.tw/handle/05122067551764087107

碩士 === 國立成功大學 === 化學系碩博士班 === 98 === At this work, five vanadium-thiolate complexes have been found and characterized. The reactivity of metal-thiolate complexes has been investigated extensively in literatures. In contrast, such chemistry has not been well explored for early-transition metal-thiolate complexes. Herein, we obtain a vanadium (III) complex, [VIII(PS2」SH)2][PPh4] (1), that can undergo nucleophilic attack toward to dichloromethane and form [VIII(PS3」)Cl][PPh4] (2) and [VIV((PS3」)2CH2)] (3). With the absence of CH2Cl2, complex 1 exhibited several types reactivity toward to dioxygen. They include metal-center oxidation, disulfide formation, and oxygenase on metal bound thiolate, leading to the formation of [VIV(PS2」SH)(PS3」)][PPh4] (4a), [VIII(P2S4」)(S-S)-][PPh4] (5) and vanadium sulfenate/disulfenate complexes, respectively. These resulting products have been identified by spectroscopies and mass spectrometry. In particular, complexes 1, 2, 3, 4a have been structurally characterized by X-ray crystallography. In addition, a {V-NO}4 compound, [V(PS3」)NO][PPh4] (6), was also isolated and characterized. The formation of this vanadium-nitrosyl species is not clear, likely from contaminated nitric acid in the reaction. Further investigation is necessary to have a better understanding of this chemistry.