Transfer of 2-Aminoethanethiolate (aet) from Nickel(II) to Cobalt(III) Coordination Sphere. Synthesis, Crystal Structure, and Some Properties of an S-Bridged Trinuclear Complex [Ni{Co(aet)2(en)}2]4+
Transfer of 2-Aminoethanethiolate (aet) from Nickel(II) to Cobalt(III) Coordination Sphere. Synthesis, Crystal Structure, and Some Properties of an S-Bridged Trinuclear Complex [Ni{Co(aet)2(en)}2]4+
复制标题
2-氨基乙硫醇 (aet) 从镍 (II) 转移到钴 (III) 配位球。
DOI：
10.1246/bcsj.68.1353
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发表时间：
1995
影响因子：
4
通讯作者：
K. Okamoto
中科院分区：
文献类型：
--
作者：
T. Konno;J. Hidaka;K. Okamoto
[CoCl 2（en）2]+与[Ni（aet）2]在水溶液中反应，生成了一个S-桥连的Co Ⅲ IIIIICo Ⅲ三核配合物[Ni{Co（aet）2（en）}2]4+（1），表明双齿-N，S配体aet从Ni Ⅱ转移到Co Ⅲ配位层. 1只形成Δ（C2-cis（S））Δ（C2-cis（S））和Λ（C2-cis（S））Λ（C2-cis（S））异构体的外消旋化合物，并通过X射线衍射分析了其晶体结构。[Ni{Co（aet）2（en）}2] Cl 4·6 H2O，化学式C12 H52 N8 O 6S 4Cl 4Co 2Ni，晶体属单斜晶系，空间群C2/c，a = 14.987（4），B = 19.480（3），c = 12.916（4）A，β = 113.67（1）°，V = 3454（1）A3，Z = 4，R = 0.046。中心NiII原子位于从正方形平面到四面体几何形状显著扭曲的环境中，由来自两个八面体C2-cis（S）-[Co（aet）2（en）]+单元的四个硫醇合硫原子配位。1的H_2O_2氧化导致Ni-S键断裂，得到单核亚磺酸根络合物[Co（NH_2CH_2CH_2SO_2-N，S）_2（en）]+（2），保留了1的C_2-cis（S）几何构型。
The reaction of [CoCl2(en)2]+ with [Ni(aet)2] in water gave an S-bridged CoIIINiIICoIII trinuclear complex, [Ni{Co(aet)2(en)}2]4+ (1), which indicates that the bidentate-N,S ligand aet transfers from the NiII to the CoIII coordination sphere. 1 formed only the racemic compound of Δ(C2-cis(S))Δ(C2-cis(S)) and Λ(C2-cis(S))Λ(C2-cis(S)) isomers, and its crystal structure was analyzed by X-ray diffraction. [Ni{Co(aet)2(en)}2]Cl4·6H2O, chemical formula C12H52N8O6S4Cl4Co2Ni, crystallizes in the monoclinic space group C2/c with a = 14.987(4), b = 19.480(3), c = 12.916(4) A, β = 113.67(1)°, V = 3454(1) A3, Z = 4, and R = 0.046. The central NiII atom is situated in an environment markedly distorted from a square-planar to a tetrahedral geometry, coordinated by four thiolato sulfur atoms from two octahedral C2-cis(S)-[Co(aet)2(en)]+ units. The H2O2 oxidation of 1 caused the cleavage of the Ni–S bonds to afford the mononuclear sulfinato complex, [Co(NH2CH2CH2SO2-N,S)2(en)]+ (2), retaining the C2-cis(S) geometry of 1....