含磷硫多牙基之鎳錯合物將磷硫多牙基與乙腈轉換成磷硫醚異核環化物之相關研究

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2007

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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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腈類水解, nitrile hydrolysis

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