一種四芽含硫配位基PS3*([P(C6H3-3-Ph-2-S)3]3-)被用來與釩三價及釩四價起始物反應，以期能夠了解高價釩硫化學的作用。在此，我們合成三種非釩氧化合物分別是: [NPent4][VIV(PS3*)(PS2*SH)](1)、 [NEt4][VIII(PS3*)Cl] (2)、[(NPr4)2][VIV(PS3*)2] (3)，並以紫外光-可見光光譜、循環電位法、核磁共振光譜加以鑑定。這些錯合物的固態結構都以X光單晶繞射儀鑑定。錯合物1具有釩四價七配位中心結構並鍵結兩個PS3*配位基，其中一個硫醇基是沒有鍵結的。錯合物2具有釩三價五配位中心結構並鍵結一個PS3*配位基以及一個氯離子。錯合物3 則具有釩四價八配位中心構結並鍵結兩個PS3*配位基。
錯合物1溶在二氯甲烷中展現親核性反應，並形成錯合物[NEt4][VIII(PS3*)Cl](2) and [VIV((PS3*)2CH2]，其中[VIV((PS3*)2CH2]的結構是由一個亞甲基置入兩個硫原子之間，從這樣的結果來看，可以了解這個反應發生是因為與釩鍵結的硫原子上具有孤對電子，並與二氯甲烷進行親核性攻擊，而詳細的機制仍然未明。
錯合物1和3對氧氣有反應性，液態暴露在空氣中時會進行氧化反應並形成錯合物[V(PS3*)2]－，但是[V(PS3*)2]－的固態產物尚未得到，而類似物質[NEt4][V(PS3”)2]已經被合成出並經過鑑定，它是以一個具有自由基的四價釩錯合物與五價釩硫錯合物的共振形式存在。

In our effort to understand high valent vanadium sulfur chemistry, a tetradentate thiolato phosphine ligand, PS3* ([P(C6H3-3-Ph-2-S)3]3-), was utilized to interacting with VIII and VIV species. As a result, three non-oxovanadium complexes were isolated. These complexes are [NPent4][VIV(PS3*)(PS2*SH)](1), [NEt4][VIII(PS3*)Cl](2) and [(NPr4)2][VIV(PS3*)2](3). These three complexes were characterized by various chemical techniques such as UV-vis-NIR Spectroscopy, Cyclic Voltammetry, and Nucleic Magnetic Resonance Spectroscopy. X-ray crystallography was also applied to obtain the structural information. Complex 1 has a hepta-coordinated vanadium(IV) center by binding to two PS3* ligand. However, one of thiolate in the title ligand remains protonated and unbound. Complex 2 has a penta-coordinate vanadium(III) center by binding to one PS3* ligand and one chloride ion. Complex 3 has an octa-coordinated vanadium(IV) center by binding to two PS3* ligand.
Complex 1 shows the reactivity towards to CH2Cl2. Dissolving the solid of 1 in CH2Cl2 led to the formation of [NEt4][VIII(PS3*)Cl](2) and [VIV((PS3*)2CH2] where a CH2 moiety was inserted to two thiolato groups . Clearly, the reaction causes the cleavage of C-Cl bond in CH2Cl2 through the nucleophilic attack of the lone-pair electrons in vanadium bound sulfur. However, the detailed mechanism remains unclear.
[NPent4][VIV(PS3*)(PS2*SH)](1) and [(NPr4)2][VIV(PS3*)2](3) also show the reactivity toward to dioxygen. The exposure of 1 and 3 in the air cause the formation of [V(PS3*)2]－ in situ. [V(PS3*)2]－ has not been isolated, however, its analogue [NEt4][V(PS3”)2] has been isolated and well characterized. [NEt4][V(PS3”)2] is identified as a resonance forms between V(V)-thiolate and V(IV)-thiyl radical species.

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