Chikamoto Yu, Kawamoto Tatsuya, Igashira-Kamiyama Asako, Konno Takumi
Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
Inorg Chem. 2005 Mar 7;44(5):1601-10. doi: 10.1021/ic048680k.
An S-bridged RhIII2PtII2 tetranuclear complex having two nonbridging thiolato groups, [{Pt(NH3)2}2{Rh(aet)3}2]4+ ([1]4+), in which two fac(S)-[Rh(aet)3] units are linked by two trans-[Pt(NH3)2]2+ moieties, was synthesized by the 1:1 reaction of fac(S)-[Rh(aet)3] (aet = 2-aminoethanethiolate) with trans-[PtCl2(NH3)2] in water. Complex [1]4+ gave both the meso (DeltaLambda) and racemic (DeltaDelta/LambdaLambda) forms, which were separated by fractional crystallization. Of two possible geometries, syn and anti, which arise from the arrangement of two nonbridging thiolato groups, the meso and racemic forms of [1]4+ selectively afforded the anti and syn geometries, respectively. The DeltaLambda-anti and DeltaDelta/LambdaLambda-syn isomers of [1]4+ reacted with Ag+ using two nonbridging thiolato groups to produce a {RhIII2PtII2AgI}n) polymeric complex, {[Ag{Pt(NH3)2}2{Rh(aet)3}2]5+}n) ([2]5+), and a RhIII2PtII2AgI pentanuclear complex, [Ag{Pt2(mu-H2O)(NH3)2}{Rh(aet)3}2]5+ ([3]5+), respectively, which contain octahedral RhIII, square-planar PtII, and linear AgI centers. In [2]5+, each DeltaLambda-anti-[{Pt(NH3)2}2{Rh(aet)3}2]4+ tetranuclear unit is bound to two AgI atoms to form a one-dimensional zigzag chain, indicating the retention of the parental S-bridged structure in DeltaLambda-anti-[1]4+. In [3]5+, two Delta- or Lambda-fac(S)-[Rh(aet)3] units are linked by a [Pt2(mu-H2O)(NH3)2]4+ dinuclear moiety, together with an AgI atom, indicating that two NH3 molecules in [1]4+ have been replaced by a water molecule that bridges two PtII centers, while the parental DeltaDelta/LambdaLambda-syn configuration is retained. The complexes obtained were characterized on the basis of electronic absorption, CD, and NMR spectra, along with single-crystal X-ray analyses.
一种具有两个非桥连硫醇盐基团的S桥连RhIII2PtII2四核配合物[{Pt(NH3)2}2{Rh(aet)3}2]4+（[1]4+），其中两个面式(S)-[Rh(aet)3]单元通过两个反式-[Pt(NH3)2]2+部分相连，通过面式(S)-[Rh(aet)3]（aet = 2-氨基乙硫醇盐）与反式-[PtCl2(NH3)2]在水中按1:1反应合成。配合物[1]4+产生了内消旋（ΔΛ）和外消旋（ΔΔ/ΛΛ）形式，通过分步结晶分离。在由两个非桥连硫醇盐基团的排列产生的两种可能几何构型（顺式和反式）中，[1]4+的内消旋和外消旋形式分别选择性地提供了反式和顺式几何构型。[1]4+的ΔΛ-反式和ΔΔ/ΛΛ-顺式异构体利用两个非桥连硫醇盐基团与Ag+反应，分别生成一种{RhIII2PtII2AgI}n)聚合物配合物{[Ag{Pt(NH3)2}2{Rh(aet)3}2]5+}n)（[2]5+）和一种RhIII2PtII2AgI五核配合物[Ag{Pt2(μ-H2O)(NH3)2}{Rh(aet)3}2]5+（[3]5+），它们包含八面体RhIII、平面正方形PtII和线性AgI中心。在[2]5+中，每个ΔΛ-反式-[{Pt(NH3)2}2{Rh(aet)3}2]4+四核单元与两个AgI原子结合形成一维锯齿链，表明在ΔΛ-反式-[1]4+中保留了母体S桥连结构。在[3]5+中，两个Δ-或Λ-面式(S)-[Rh(aet)3]单元通过一个[Pt2(μ-H2O)(NH3)2]4+双核部分以及一个AgI原子相连，这表明[1]4+中的两个NH3分子已被一个桥连两个PtII中心的水分子取代，同时保留了母体ΔΔ/ΛΛ-顺式构型。所得到的配合物通过电子吸收光谱、圆二色光谱和核磁共振光谱以及单晶X射线分析进行了表征。
