中文摘要
我們利用P(C6H5)(o-C6H4SH)2 (PS2)和P(C6H5)2(o-C6H4SH) (PS1)分別與[Ni(CH3CN)6](ClO4)2在乙腈或丙腈溶劑下反應，可得[Ni(P(C6H5)(o-C6H4S)(o-C6H4SC(CH3)NH2)2)](ClO4)2 (1)、[Ni(P(C6H5)(o- C6H4S)(o-C6H4SC(CH3CH2)NH2)2)](ClO4)2 (2)、[Ni2(P(C6H5)(o-C6H4S)2)] (4)、(P((o-C6H4SC(CH3)NH3)(C6H5)2))(ClO4)2 (5)等四種化合物，然而在合成錯合物1及2的過程中，會產生[Ni(P(C6H5)(o-C6H4S)(o-C6H4SH))2] (3)；從結構上發現錯合物1、2含有由乙腈轉換來的硫亞胺酯，與腈水解酶催化機制中產生的酵素鍵結-醯胺硫醚中間物結構相似，而化合物5含有由乙腈轉換來的硫胺基，同樣也類似腈水解酶催化機制中產生的中間物。另外，在與上述類似的反應條件下加入10倍量之60%的過氯酸水溶液後，經分離可得到錯合物4和(P(o-C6H4SC(CH3)NHCOCH2CH3)- (C6H5)(o-C6H4SH))(ClO4) (7) (在丙腈中反應)或錯合物4 和(P(o-C6H4SCH3)NHCOCH3)(C6H5)(o-C6H4SH))(ClO4) (8) (在乙腈中反應)。藉由一連串的實驗結果，推測錯合物1和4可能是將乙腈及PS2活化進而得到化合物8及NH4ClO4的催化劑。故將PS2和60% 的過氯酸水溶液反應分別加入少量的錯合物1或4反應，所得到的實驗結果發現由錯合物1進行催化反應可得化合物8的產率增加為2倍，而由錯合物4催化可得3倍的化合物8。在相似反應條件下，當PS1與60 %的過氯酸水溶液在乙腈溶劑下反應20 ~ 30天，其結果和之前實驗成果不同，可得到[O=P(C6H5)2(o-C6H4S)]2 (6)、NH4ClO4和CH3COOH。

Abstract
Two ligands, P(C6H5)(o-C6H4SH)2 (PS2) and P(C6H5)2(o-C6H4SH) (PS1), were employed to react with [Ni(CH3CN)6](ClO4)2 in acetonitrile or propionitrile to form three nickel complexes, [Ni(P(C6H5)(o-C6H4S)(o- C6H4SC(CH3)NH2)2)](ClO4)2 (1), [Ni(P(C6H5)(o-C6H4S)(o-C6H4SC(CH3- CH2)NH2)2)](ClO4)2 (2), and [Ni2(P(C6H5)(o-C6H4S)2)] (4), and a heterocycle phosphine of (P((o-C6H4SC(CH3)NH3)(C6H5)2))(ClO4)2 (5). The conversion of acetonitrile or propionitrile to thioimino ester on the mercapto phosphine ligands of nickel complexes 1 and 2 were observed. The resulting thioimino ester groups of these conversions are similar to the intermediate proposed in the catalytic mechanism of nitrilase. In the previous reactions, which producing complexe 1 or 2, an intermediate, [Ni(P(C6H5)(o-C6H4S)(o- C6H4SH))2] (3), was formed first, and precipitated as a green solid. The uncoordinated thiol groups of complex 3 will attack the unsaturated carbon of nitriles, to generate complex 1 in acetonitrile or to form complex 2 in propionitrile. By adding tenfold HClO4(aq) (60 %) to a nitrile solution of complex 1, compound 4 and P((o-C6H4SC(CH3)NHCOCH2CH3)(C6H5)(o- C6H4SH))(ClO4) (7) (in propionitrile), or compound 4 and P[(o-C6H4SC(CH3)NHCOCH3)(C6H5)(o-C6H4SH)](ClO4) (8) (in acetonitrile) were produced. From the formation of compound 8 and NH4ClO4 in acetonitrile, complexes 1 and 4 were considered to be the catalysts for the reactions mentioned above. Our study for this catalytic reaction shows the yield of product 8 increasing about 2 fold by complex 1, and 3 fold by complex 4. As PS1 reacted with HClO4(aq) (60 %) in acetonitrile for 20 ~ 30 days, [O=P(C6H5)2(o-C6H4S)]2 (6), NH4ClO4, and CH3COOH were isolated. The resulting products are different from those produced by the reaction of PS2.

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