不論是在生物體上或是醫學方面，具有硫官能基的化合物，如生物體上的半胱胺酸(cysteine)及榖胱甘214(glutathione)，與高價釩之間的交互作用成為研究上必要的主題，目前藉由模擬相似於半胱胺酸(cysteine)及榖胱甘214(glutathione)的官能基，來研究含硫配位基與高價釩間的化學反應，間接來了解生物體釩硫間的氧化還原反應的過程，在我們的研究裡，使用VVO(i-PrO)3與PS3(tristhiolatophosphine)系列配位基作為研究對象，而PS3系列配位基分別為[PS3]H3、[PS3’]H3及[PS3”]H3 {[PS3]H3 = P(C6H4-2-SH)3、[PS3’]H3= P(C6H3-5-Me-2-SH)3及[PS3”]H3 = P(C6H3-3-SiMe3-2-SH)3)}。

　　在研究中，我們獲得了化合物[VIV2(m-OMe)3(PS3”)][Ph4P] (1)、[VVO(PS3”)(OCH3)][Ph4P] (2)、[VIV(PS3’’)2][(C2H5)4N] (3)、[VIV(PS3)2(S-S)] (4a)、[VIV(PS3’)2(S-S)] (4b) 及 [VIV(PS3’)(PS3’SMe)][(C2H5)4N] (5a)。

　　化合物(1)為四價雙核非釩氧(nonoxovanadium)化合物，而每一個釩中心皆為七配位，釩與釩間以甲氧基(-OCH3)作為架橋。化合物(2)的釩中心與一個PS3’’及一個甲氧基(-OCH3)鍵結，形成六配位釩氧(oxovanadium)化合物。化合物(3)是由兩個PS3’’以螯合方式與釩鍵結，形成八配位化合物，且其為四價非釩氧(nonoxovanadium)化合物。化合物(4a)及(4b)分別由兩個PS3及兩個PS3’以螯合方式與釩鍵結，形成六配位化合物，其中配位基間會形成一個雙硫鍵。化合物(5a)是由一個PS3’與一個PS3’SMe以螯合方式與釩鍵結，形成七配位化合物，且其為四價非釩氧(nonoxovanadium)化合物。在VVO(i-PrO)3 與PS3(tristhiolatophosphine) 系列配位基反應中，我們獲得了五價或四價不同配位數的化合物，由於這樣的多樣變化性，提供了釩與硫間的氧化還原特性的研究價值。

　　在此論文中，我們敘述化合物(1)~(5a)的結構及合成方法，並探討這些化合物的數據如光譜及磁性。

　The interactions of high valent vanadium species with sulfur containing bioligands such as cysteine and glutathione are essential subjects in various biological and medical aspects. Efforts have been made on understanding fundamental chemistry of high valent vanadium complexes with thiolato ligands that have similar functional groups to those in cysteine and glutathione. In this work, the chemistry of tristhiolatophosphine ligands, [PS3]H3, [PS3’]H3 and [PS3”]H3 ([PS3]H3 = P(C6H4-2-SH)3, [PS3’]H3 = P(C6H3-5-Me-2-SH)3, [PS3”]H3 = P(C6H3-3-SiMe3-2-SH)3), reacting with VVO(O-i-Pr)3 were investigated.

　The reactions led to the formation of [VIV2(m-OMe)3(PS3”)][Ph4P] (1) , [VⅤO(PS3”)(OCH3)][Ph4P] (2), [VIV(PS3’’)2][(C2H5)4N] (3), [VIV(PS3)2(S-S)] (4a) [VIV(PS3’)2(S-S)] (4b) and [VIV(PS3’)(PS3’SMe)][(C2H5)4N] (5a).

　Compound (1) is a dinuclear nonoxovanadium(IV) species with two seven-coordinate vanadium centers bridging by three methoxides. Compound (2) has a six-coordinate oxovanadium(V) center binding to a PS3’’ ligand and a methoxide. Compound (3) has an eight-coordinate nonoxovanadium(IV) center binding to two PS3” ligands. Compound (4a) ~ (4b) are nonoxovanadium(IV) species binding to two PS3 ligands, where a disulfide forms between two ligated PS3 ligands. Comound (5a) has a seven-coordinate vanadium center binding to a PS3’ ligand and a PS3’SMe, a bis(thiolato)thioether phosphine ligand. The generation of versatile complexes, (1) ~ (5a), in the reaction of VO3+ with tristhiolatophosphine ligands system, is attributed to the occurrence of the redox chemistry between V(V)/V(IV) and thiolate/thiyl-radical couples.

　Herein, we detail the syntheses, structures of (1) ~ (5a), as well as the spectroscopic and magnetic studies of these complexes.

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