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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。
This paper reports the nucleophilic effects of iodine ions on the unstable Ni (Ⅱ) -S (arylthiolate) bond such that Fe (CO) 4I2 and Ni (SR) 2 ) NiI2 (dppe) Ni-Ni binuclear complex [(dppe) Ni (μ-I) (μ-pdt) Ni (dppe)] containing iodine and diarylthiolate ion- (Dppe)] and [Ni (pdt) (dppe)] or [Ni (edt) dppe)] in methylene chloride; this type of reaction is believed to be due to the attack of the Ni-I bond by the lone pair of electrons on the S-donor in the thiolate group We observe that the reaction of [FeCp (CO) 2I] and [Ni (pdt) (dppe)] or [Ni (edt) (dppe)] in dichloromethane is extremely slow; however, when the above reaction After the metathesis displacement of NH4PF6, the Ni-Ni binuclear complex [(dppe) Ni (μ-Ni-Ni) The experimental results demonstrate that the nickel (Ⅱ) -porphyrins and the nickel (Ⅱ) -porphyrins of nickel (dppe) Reactivity of Ni (Ⅱ) -S Bonds in Thiolate Ion - Phosphine Complexes Bridging the second metal ion and iodide ion different cell change.