Preparation, stereochemistry, and reactivity of linear-type S-bridged MCrIIIM (M=RhIII, IrIII) trinuclear complexes with 2-aminoethanethiolate (aet).: Crystal structures of ΔΛ-[Cr{M(aet)3}2]3+
Preparation, stereochemistry, and reactivity of linear-type S-bridged MCrIIIM (M=RhIII, IrIII) trinuclear complexes with 2-aminoethanethiolate (aet).: Crystal structures of ΔΛ-[Cr{M(aet)3}2]3+
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DOI：
10.1246/bcsj.71.661
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发表时间：
1998-03-01
影响因子：
4
通讯作者：
Okamoto, K
中科院分区：
文献类型：
--
作者：
Miyashita, Y;Sakagami, N;Okamoto, K
S桥三核配合物。[C-III（M（aet）（3））（3+），（M = Rh-III（1），Ir-III（2）; aet = NH_2CH_2CH_2S-）由fac（S）-[M（aet）（3）]与Cr_2O_3反应合成。将它们分离并光学拆分成Delta Delta、Lambda Delta和Delta Lambda异构体。在1和2的这些异构体中，通过X射线衍射法测定Δ λ异构体（1a和2a）的晶体结构。Ia和2a中的每一个由两个Sac（S）-[M（aet）（3）]亚基、中心Cr原子、三个硝酸盐和三个水分子[Cr（M（aet）（3）}（2）]（NO3）（3）组成。3 H（2）O，其中三种金属排列成精确的线性。中心Cr原子与（CrS 6）-S-III发色团位于八面体环境中，该发色团由两个末端fac（S）-[M（aet）（3）]单元配位形成。1和2的其他异构体的特征在于通过吸收和CD光谱，摩尔电导率，和磁化率。Δ λ-[Cr{M（aet）（3）}（2）]（3+）在水中的每个循环伏安图显示可逆的氧化还原对（M（IV）/M（III））和不可逆的还原波（Cr（III）/Cr（II））。还讨论了S-桥连（MCrM）-M-III配合物的稳定性与Cr-S键强度的关系。
S-Bridged trinuclear complexes. [C-III(M(aet)(3)}(2))(3+), (M = Rh-III (1), Ir-III (2); aet = NH2CH2CH2S-) were newly prepared by the reaction of fac(S)-[M(aet)(3)] with chromium(III) nitrate. They were separated and optically resolved into the Delta Delta, Lambda Delta, and Delta Lambda isomers. Of these isomers for 1 and 2, the crystal structures of the Delta Lambda isomers (1a and 2a) were determined by an X-ray diffraction method. Each of la and 2a consists of two Sac(S)-[M(aet)(3)] subunits, a central Cr atom, three nitrates, and three water molecules, [Cr(M(aet)(3)}(2)](NO3)(3) . 3H(2)O, in which three metals are aligned so as to be exactly linear. The central Cr atom is situated in an octahedral environment with the (CrS6)-S-III chromophore, which is formed by the coordination of two terminal fac(S)-[M(aet)(3)] units. The other isomers for 1 and 2 were characterized by the absorption and CD spectra, the molar conductivity, and the magnetic susceptibility. Each cyclic voltammogram of Delta Lambda -[Cr{M(aet)(3)}(2)](3+) in water showed a reversible redox couple (M(IV)/M(III)) and an irreversible reduction wave (Cr(III)/Cr(II)). The stabilities of the S-bridged (MCrM)-M-III complexes are also discussed in relation to the Cr-S bond strengths.