Synthesis, structure and oxidation of [NiL1]2+[L1= 5-(4-amino-2-azabutyl)-5-methyl-3,7-diazanonane-1,9-diamine]: evidence for rearrangement within the complexed nickel(III) species
作者:Alexander McAuley、Seth Subramanian、Todd W. Whitcombe
DOI:10.1039/dt9930002209
日期:——
7-diazanonane-1,9-diamine, L1, has been synthesised and a nickel(II) complex, [NiL1]Br2, characterized by X-ray crystallography (monoclinic, space group P21/n, a= 14.143, b= 9.618, c= 13.552, β= 106.14°, Z= 4, R= 0.0429, R′= 0.0418). The Cation adopts a distorted octahedral geometry typical of similar nickel(II) complexes. The complex [NiL1]2+ can be oxidized, under unutral conditions, either electrochemically
合成了配体5-(4-氨基-2-氮杂丁基)-5-甲基-3,7-二氮杂壬烷-1,9-二胺L 1和镍(II)络合物[NiL 1 ] Br 2。,其特征在于通过X射线晶体(单斜晶系,空间群P 2 1 / ñ,一个= 14.143,b = 9.618,c ^ = 13.552,β= 106.14°,ž = 4,- [R = 0.0429,- [R '= 0.0418)。阳离子采用类似镍(II)配合物的典型变形的八面体几何形状。复合物[NiL 1 ] 2+可以在非常规条件下被电化学或通过使用S 2 O 8 2–氧化成中等稳定的镍(III)配合物。通过使用ESR光谱监测S 2 O 8 2–的反应,已经获得了具有特征性ESR信号的三种物种g 1,g 2和g 3的证据。这些代表初始镍(III)络合离子和通过硫酸盐取代形成的两个结构修饰。最终产物是扭曲的四方配合物,带有轴向硫酸盐连接。这些反应代表在NiN 6