含磷硫多牙基之正四價鎳錯合物合成及其光譜探討

張智凱

指導教授 ： 李位仁

國立臺灣師範大學/理學院/化學系/碩士(2010年)

摘要

由[Ni(CH3CN)6](ClO4)2與兩當量的P(C6H5)(o-C6H4SH)2 (PS2H2)在乙腈下進行反應會得到綠色Ni(P(C6H5)(o-C6H4S)(o-C6H4SH))2 (1)。而值得注意的是，當整個反應攪拌隔夜後，則會有黃綠色的[Ni(P(C6H5)(o-C6H4S)(o-C6H4SC(CH3)NH2)2)](ClO4)2 (2)產生。從錯合物2的結構上可看出PS2H2之硫醇會與乙腈結合形成硫亞胺酯的結構。
正四價的鎳錯合物Ni(P(C6H5)(o-C6H4S)2)2 (3)可成功地由錯合物1進行氧化反應而得到。據我們所知，此錯合物也是第一個在空氣下穩定的Ni(IV)的化合物其上有兩個PS22-配位。而本研究中所關注的焦點是要了解錯合物3如何生成，此化合物必須在氧氣和NEt3同時存在的環境下產生。事實上，錯合物3可由錯合物1和2進行製備而得到。另外，在沒有氧氣的環境下，將錯合物1和一或兩當量的NEt3進行反應，會產生在PS2H-的兩個硫之間有CH架橋的錯合物Ni2(P2(C6H5)2(o-C6H4S)2(o-C6H4S-μ-CH2-o-C6H4S)) (4)。當錯合物2和四當量的NEt進行反應，則會得到已知的雙鎳核錯合物[Ni(P(C6H5)(o-C6H4S)(μ-o-C6H4S))]2 (5)。此外，一個disulfide錯合物[Ni(P(C6H5)(o-C6H4S)(μ-o-C6H4S))2]n/2∙n/2[Ni(P(C6H5)2(o-C6H4S))2] (6)則是由錯合物5和兩當量的P(C6H5)(o-C6H4SH)2 (PS1H)進行反應而生成。

關鍵字

鎳錯合物

並列摘要

Reaction of [Ni(CH3CN)6](ClO4)2 and two equiv of P(C6H5)(o-C6H4SH)2 (PS2H2) in acetonitrile gave a green product of Ni(P(C6H5)(o-C6H4S)(o-C6H4SH))2 (1). Noteworthily, a yellow-brown product of [Ni(P(C6H5)(o-C6H4S)(o-C6H4SC(CH3)NH2)2)](ClO4)2 (2), was formed when the above reaction was stirred overnight. The structure of complex 2 revealed the incorporation of acetonitrile molecules with thiol groups of PS2H- ligands in complex 1 to form thioiminoester groups.
A Ni(IV) complex, Ni(P(C6H5)(o-C6H4S)2)2 (3), was successfully produced from the oxidation of complex 1. This is the first air-stable Ni(IV) species coordinated by two PS22- ligands. In this study, we focused on the generation of complex 3, which was formed in the presence of oxygen and NEt3. In fact, complex 3 can be prepared from both complexes 1 and 2. If complex 1 only reacted with one or two equiv of NEt3 without oxygen in CH2Cl2, a new compound, Ni(P2(C6H5)2(o-C6H4S)2(o-C6H4S-μ-CH2-o-C6H4S)) (4) with a CH2 group between two sulfurs from PS2H-, was produced. Reaction of complex 2 with four equiv of NEt3 generated a known dinickel complex, [Ni(P(C6H5)(o-C6H4S)(μ-o-C6H4S))]2 (5). In addition, a new disulfide compound, [Ni(P(C6H5)(o-C6H4S)(μ-o-C6H4S))2]n/2∙n/2[Ni(P(C6H5)2(o-C6H4S))2] (6), was produced by the reaction of complex 5 with two equiv of P(C6H5)2(o-C6H4SH) (PS1H).

參考文獻

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