Structure and Properties of Lantern-Shaped Hexapalladium Complexes with Germylene and Thiolate Ligands [Pd6(μ-GePh2)2(μ-SC6H4-p-X)2(CN-C6H3Me2-2,6)8] (X = NO2, Cl, H, CH3)
Structure and Properties of Lantern-Shaped Hexapalladium Complexes with Germylene and Thiolate Ligands [Pd6(μ-GePh2)2(μ-SC6H4-p-X)2(CN-C6H3Me2-2,6)8] (X = NO2, Cl, H, CH3)
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DOI：
10.1002/ejic.202000233
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发表时间：
2020-06-03
影响因子：
2.3
通讯作者：
Osakada, Kohtaro
中科院分区：
文献类型：
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作者：
Koizumi, Take-aki;Tsuchido, Yoshitaka;Osakada, Kohtaro
二芳基二硫化物 ArSSAr (Ar = C6H4-p-Cl, Ph, C6H4-p-CH3) 与具有桥联亚甲锗烷基配体的六钯配合物 [Pd-6(mu-GePh2)(2)(CN-C6H3Me2-2,6)(8)(mu-CN-C6H3Me2-2,6)(2)] (1) 反应，得到 芳基硫醇盐桥配合物，[Pd-6(mu-GePh2)(2)(mu-SAr)(2)(CN-C6H3Me2-2,6)(8)] (Ar = C6H4-p-Cl, Ph, C6H4-p-CH3) (3-5)。 (Pd4Pd2(I))-Pd-(0) 配合物以及与 4-硝基苯硫醇配体的类似配合物 [Pd-6(mu-GePh2)(2)(mu-SC6H4-p-NO2)(2)(CN-C6H3Me2-2,6)(8)] (2) 具有六角双锥体结构，其中包含两个桥连 硫醇盐配体位于基础配位位点。 2-5的电化学测量显示氧化区域中E-1/2 = -0.51 (2)、-0.61 (3)、-0.66 (4)和-0.70 (5) V (vs. Fc(+)/Fc)处出现一个可逆氧化还原波，并且在E-pc = -2.04 (2)、-2.29 (3)和-2.38 (4)处出现不可逆还原峰 V（相对于 Fc(+)/Fc）在还原区域。氧化电位和还原电位均与硫醇盐配体芳基的哈米特取代常数 sigma(p) 密切相关。
Reaction of diaryl disulfides, ArSSAr (Ar = C6H4-p-Cl, Ph, C6H4-p-CH3) with a hexapalladium complex with bridging germylene ligands, [Pd-6(mu-GePh2)(2)(CN-C6H3Me2-2,6)(8)(mu-CN-C6H3Me2-2,6)(2)] (1) afforded arylthiolate-bridged complexes, [Pd-6(mu-GePh2)(2)(mu-SAr)(2)(CN-C6H3Me2-2,6)(8)] (Ar = C6H4-p-Cl, Ph, C6H4-p-CH3) (3-5). The (Pd4Pd2(I))-Pd-(0) complexes as well as analogous complex with 4-nitrophenylthiolate ligands [Pd-6(mu-GePh2)(2)(mu-SC6H4-p-NO2)(2)(CN-C6H3Me2-2,6)(8)] (2) have a hexagonal bipyramidal structure which contains two bridging thiolate ligands at basal coordination sites. Electrochemical measurement of 2-5 showed one reversible redox wave at E-1/2 = -0.51 (2), -0.61 (3), -0.66 (4) and -0.70 (5) V (vs. Fc(+)/Fc) in the oxidation region, and irreversible reduction peak at E-pc = -2.04 (2), -2.29 (3), and -2.38 (4) V (vs. Fc(+)/Fc) in the reduction region. Both oxidation and reduction potentials are correlated well with Hammett substitution constant sigma(p) of the aryl group of the thiolate ligands.