Chikamoto Yu, Hirotsu Masakazu, Yamaguchi Tadashi, Yoshimura Takashi, Konno Takumi
Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Japan.
Dalton Trans. 2004 Nov 7(21):3654-61. doi: 10.1039/b409614b. Epub 2004 Oct 4.
The reaction of fac(S)-[Co(aet)(3)](aet = aminoethanethiolate) with PdCl(4) in a 2:1 ratio in water gave an S-bridged Co(III)Pd(II)Co(III) trinuclear complex composed of two mer(S)-[Co(aet)(3)] units, PdCo(aet)(3)(1). In 1, each of the two mer(S)-[Co(aet)(3)] units is bound to a square-planar Pd(II) ion through two of three thiolato groups, leaving two non-bridging thiolato groups at the terminal. Of two geometrical forms, syn and anti, possible for PdCo(aet)(3), which arise from the difference in arrangement of two terminal non-bridging thiolato groups, 1 afforded only the syn form. A similar reaction of fac(S)-[Co(aet)(3)] with PtCl(4) or trans-[PtCl(2)(NH(3))(2)] produced an analogous Co(III)Pt(II)Co(III) trinuclear complex, PtCo(aet)(3)(2), but both the syn and anti forms were formed for 2. Complexes 1 and syn- and anti-2, which exclusively exist as a racemic(DeltaDelta/LambdaLambda) form, were successfully optically resolved with use of Sb(2)(R,R-tartrato)(2) as the resolving agent. The reaction of syn-2 with [AuCl[S(CH(2)CH(2)OH)(2)]] led to the formation of an S-bridged Co(III)(4)Pt(II)(2)Au(I)(2) octanuclear metallacycle, [Au(2)PtCo(aet)(3)](6+)(3), while the corresponding reaction of anti-2 afforded a different product (4) that is assumed to have a polymeric structure in [[Au[PtCo(aet)(3)]](3+)](n).
在水中，顺式（S）-[Co（aet）₃]（aet = 氨基乙硫醇盐）与[PdCl₄]²⁻以2:1的比例反应，生成了一种由两个面式（S）-[Co（aet）₃]单元组成的S桥连Co（III）Pd（II）Co（III）三核配合物，[Pd[Co（aet）₃]₂]²⁺（[1]²⁺）。在[1]²⁺中，两个面式（S）-[Co（aet）₃]单元中的每一个都通过三个硫醇盐基团中的两个与平面正方形的Pd（II）离子相连，在末端留下两个非桥连硫醇盐基团。对于[Pd[Co（aet）₃]₂]²⁺可能存在的顺式和反式两种几何异构体，它们是由两个末端非桥连硫醇盐基团排列方式的差异产生的，[1]²⁺只得到了顺式异构体。顺式（S）-[Co（aet）₃]与[PtCl₄]²⁻或反式-[PtCl₂（NH₃）₂]的类似反应产生了类似的Co（III）Pt（II）Co（III）三核配合物，[Pt[Co（aet）₃]₂]²⁺（[2]²⁺），但[2]²⁺同时形成了顺式和反式两种异构体。配合物[1]²⁺以及顺式和反式[2]²⁺仅以外消旋（ΔΔ/ΛΛ）形式存在，使用[Sb₂（R，R-酒石酸根）₂]²⁻作为拆分剂成功地对它们进行了光学拆分。顺式-[2]²⁺与[AuCl[S（CH₂CH₂OH）₂]]反应生成了一种S桥连的Co（III）₄Pt（II）₂Au（I）₂八核金属环，[Au₂[Pt[Co（aet）₃]₂]₂]⁶⁺（[3]⁶⁺），而反式-[2]²⁺的相应反应得到了一种不同的产物（[[4]³⁺]ₙ），据推测在[[Au[Pt[Co（aet）₃]₂]]³⁺]ₙ中具有聚合结构。
