通过镍(Ⅱ)-硫键和碘离子基元反应有理合成碘-二硫醇盐桥联的双核镍-镍配合物(英文)  

Rational preparation of iodide-dithiolate-bridged binuclear Ni-Ni complex from the reaction between nickel(Ⅱ)-sulfur bond and iodide moiety

作　　者：王强[1,2] 安德鲁.马 朱文锋 亚力山大.布雷克 克莱尔.威尔森 斯蒂芬.戴维斯 马丁.施罗德 

机构地区：[1]诺丁汉大学化学学院 [2]武汉科技学院环境科学研究所,湖北武汉430073

出　　处：《武汉科技学院学报》2008年第8期70-77,共8页Journal of Wuhan Institute of Science and Technology

基　　金：Supported by BBSRC(UK);University of Nottingham and the CVCP(ORS Awards Scheme)(for Q.W);the Royal Society Sino-British Fellowship(for W.F.Zhu)~~

摘　　要：本文报道由于碘离子对不稳定的Ni(Ⅱ)-S(芳基硫醇盐)键的亲核作用,使得Fe(CO)4I2和Ni(SR)2(dppe(SR=芳基硫醇盐)之间的反应生成NiI2(dppe)。含碘和二芳基硫醇盐离子桥联的Ni-Ni双核配合物[(dppe)Ni(μ-I)(μ-pdt)Ni(dppe)]I和[(dppe)Ni(μ-I)(μ-edt)Ni(dppe)]I可方便地由[NiI2(dppe)]和[Ni(pdt)(dppe)]或[Ni(edt)(dppe)]在二氯甲烷的溶液中的反应制得;该类反应可认为是由于硫醇盐离子基团中S-供体上的孤对电子对Ni-I键的进攻所致。另一方面,我们观察到[FeCp(CO)2I]和[Ni(pdt)(dppe)]或[Ni(edt)(dppe)]在二氯甲烷中的反应极其缓慢;但当向上述反应体系中加入NH4PF6进行复分解置换后,源于碘离子和Ni(Ⅱ)-S键的作用同样可得到含碘与二芳基硫醇盐离子桥联的Ni-Ni双核配合物[(dppe)Ni(μ-I)(μ-pdt)Ni(dppe)]PF6和[(dppe)Ni(μ-I)(μ-edt)Ni(dppe)]PF6。实验结果说明在本文所讨认的镍(Ⅱ)-硫醇盐离子-膦配合物中,Ni(Ⅱ)-S键的反应活性随桥联的第二金属离子和不同的碘离子基元而改变。The reaction between Fe（CO）4I2 and Ni（SR）2（dppe） affords NiI2（dppe） due to the necleophilic attack of iodide on the labile N-S（aryl thiolate） bonds. The iodide-dithiolate-bridged binuclear Ni-Ni complexes [（dppe）Ni（μ-I）（μ-pdt）Ni（dppe）]I and [（dppe）Ni（μ-I）（μ-edt）Ni（dppe）]I Can be readily prepared by reaction between [NiI2（dppe）] and [Ni（pdt）（dppe）] or [Ni（edt）（dppe）] [dppe = 1,2-his （diphenyl phosphino）-ethane; pdt = 1,3-propane-dithiolate; edt = 1,2-ethane-dithiolate] in CH2C12 as a result of the attack on the Ni-I bond by the lone pairs of electrons on thiolato sulfur donors. On the other hand, the reaction between [FeCp（CO）2I] and [Ni（pdt）（dppe）] or [Ni（edt）（dppe）] in CH2C12 processes extremely slow. However, upon the metathesis with NH4PF6 for these reaction, the iodide-thiolate-bridged binuclear Ni-Ni complexes [（dppe）Ni（μ-I）（μ-pdt）Ni（dppe）]PF6 and [（dppe）Ni（μ-I）（μ-edt）Ni（dppe）]PF6 have been prepared due to the reaction of iodide and the Ni（Ⅱ）-S bonds. These results suggest that the reactivity of Ni-SR bonds in such Ni-thiolate-phosphine complexes is tuneable with regard to the second metal ion and the different reactivity of iodide moiety.

关 键 词：镍 硫醇盐 双核配合物 镍-硫醇盐-碘配合物 

分 类 号：O614[理学—无机化学]