Sulfur-bridged Co(III)Pt(II)Co(III) trinuclear complexes with mixed aliphatic and aromatic thiolate ligands: effect of nonbridging ligands on the homochiral linkage of cobalt(III) octahedrons by platinum(II).
Sulfur-bridged Co(III)Pt(II)Co(III) trinuclear complexes with mixed aliphatic and aromatic thiolate ligands: effect of nonbridging ligands on the homochiral linkage of cobalt(III) octahedrons by platinum(II).
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具有混合脂肪族和芳香族硫醇盐配体的硫桥联Co(III)Pt(II)Co(III)三核配合物：非桥联配体对铂(II)与钴(III)八面体同手性连接的影响。
DOI：
10.1021/ic0303338
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发表时间：
2004
影响因子：
4.6
通讯作者：
T. Konno
中科院分区：
文献类型：
--
作者：
M. Hirotsu;R. Endo;T. Yoshimura;T. Konno
[Ni[Co（aet）（2）（pyt）]（2）]（2+）（aet = 2-氨基乙硫醇盐，pyt = 2-吡啶乙硫醇盐）与[PtCl（4）]（2）（-）反应，得到由两个[Co（aet）（2）（pyt）]单元组成的S-桥连Co（III）Pt（II）Co（III）三核配合物[Pt[Co（aet）（2）（pyt）]（2）]（2+）（[1]（2+））。当1：1 [Ni][Co]的混合物（aet）（2）（pyt）]（2）]（2+）和[Ni[Co（aet）（2）（en）]（2）]（4+）与[PtCl（4）]（2）（-）反应，一种混合型S-桥连Co（III）Pt（II）Co（III）配合物，由一个[Co（aet）（2）（pyt）]和一个[Co（aet）（2）（en）]（+）单位，[Pt[Co（aet）（2）（en）][Co（aet）（2）（pyt）]（3+）（[2]（3+）），以及[1]（2+）和[Pt[Co（aet）（2）（en）]（2）]（4+）。合成了相应的含Pymt的Co（III）Pt（II）Co（III）三核配合物（2-嘧啶硫醇盐），[Pt[Co（aet）（2）（pymt）]（2）]（2+）（[3]（2+））和[Pt[Co（aet）（2）（en）][Co（aet）（2）（pymt）]]（3+）（[4]（3+）），使用[Ni[Co（aet）（2）（pyt）]（2）]（2+）代替[Ni[Co（aet）（2）（pyt）]（2）]（2+）。而[Pt[Co（aet）（2）（en）]（2）]（4+）则以约100：1的比例同时形成δ-内酰胺（内消旋）和δ-内酰胺/δ-内酰胺（外消旋）。1：1时，[1]（2+）（ca. deltalambda：deltadelta/deltalambda = 1：3）和[2]（3+）（ca. delta（en）lambda（pyt）/lambda（en）delta（pyt）：delta（en）lambda（pyt）/delta（en）lambda（pyt）= 1：2）。此外，[3]（2+）和[4]（3+）主要形成三角形/三角形。这些结果表明，由两个八面体[Co（aet）（2）（L）]（0或+）单元组成的S-桥联Co（III）Pt（II）Co（III）三核配合物的纯手性选择性按L = en < pyt < pymt的顺序增强。通过X射线衍射分析确定了中间型δ-[1]Cl（2）·4 H（2）O和自发分解的δ-[4]（ClO（4））（3）·H（2）O的晶体结构。在δ-[1]（2+）中，δ和λ构型的mer（S）. transs（N（aet））-[Co（aet）（2）（pyt）]单元通过四个aet S原子被正方形平面的Pt（II）离子连接，形成线型S-桥连三核结构。在deltadelta-[4]（3+）中，类似的线性型三核结构由delta-mer（S）. transs（N（aet））-[Co（aet）（2）（pymt）]和delta-C（2）-cis（S）-[Co（aet）（2）（en）]（+）单元构成，这些单元通过四个aet S原子以略微扭曲的正方形平面几何形状与Pt（II）离子结合。
The reaction of [Ni[Co(aet)(2)(pyt)](2)](2+) (aet = 2-aminoethanethiolate, pyt = 2-pyridinethiolate) with [PtCl(4)](2)(-) gave an S-bridged Co(III)Pt(II)Co(III) trinuclear complex composed of two [Co(aet)(2)(pyt)] units, [Pt[Co(aet)(2)(pyt)](2)](2+) ([1](2+)). When a 1:1 mixture of [Ni[Co(aet)(2)(pyt)](2)](2+) and [Ni[Co(aet)(2)(en)](2)](4+) was reacted with [PtCl(4)](2)(-), a mixed-type S-bridged Co(III)Pt(II)Co(III) complex composed of one [Co(aet)(2)(pyt)] and one [Co(aet)(2)(en)](+) units, [Pt[Co(aet)(2)(en)][Co(aet)(2)(pyt)]](3+) ([2](3+)), was produced, together with [1](2+) and [Pt[Co(aet)(2)(en)](2)](4+). The corresponding Co(III)Pt(II)Co(III) trinuclear complexes containing pymt (2-pyrimidinethiolate), [Pt[Co(aet)(2)(pymt)](2)](2+) ([3](2+)) and [Pt[Co(aet)(2)(en)][Co(aet)(2)(pymt)]](3+) ([4](3+)), were also obtained by similar reactions, using [Ni[Co(aet)(2)(pymt)](2)](2+) instead of [Ni[Co(aet)(2)(pyt)](2)](2+). While [Pt[Co(aet)(2)(en)](2)](4+) formed both the deltalambda (meso) and deltadelta/lambdalambda (racemic) forms in a ratio of ca. 1:1, the preferential formation of the deltadelta/lambdalambda form was observed for [1](2+) (ca. deltalambda:deltadelta/lambdalambda = 1:3) and [2](3+) (ca. delta(en)lambda(pyt)/lambda(en)delta(pyt):deltadelta/lambdalambda = 1:2). Furthermore, [3](2+) and [4](3+) predominantly formed the deltadelta/lambdalambda form. These results indicate that the homochiral selectivity for the S-bridged Co(III)Pt(II)Co(III) trinuclear complexes composed of two octahedral [Co(aet)(2)(L)](0 or +) units is enhanced in the order L = en < pyt < pymt. The isomers produced were separated and optically resolved, and the crystal structures of the meso-type deltalambda-[1]Cl(2).4H(2)O and the spontaneously resolved deltadelta-[4](ClO(4))(3).H(2)O were determined by X-ray analyses. In deltalambda-[1](2+), the delta and Lambda configurational mer(S).trans(N(aet))-[Co(aet)(2)(pyt)] units are linked by a square-planar Pt(II) ion through four aet S atoms to form a linear-type S-bridged trinuclear structure. In deltadelta-[4](3+), a similar linear-type trinuclear structure is constructed from the delta-mer(S).trans(N(aet))-[Co(aet)(2)(pymt)] and delta-C(2)-cis(S)-[Co(aet)(2)(en)](+) units that are bound by a Pt(II) ion with a slightly distorted square-planar geometry through four aet S atoms.