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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Structure and properties of bivalent nickel and copper complexes with pyrazine-amide-thioether coordination: stabilization of trivalent nickel
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Structure and properties of bivalent nickel and copper complexes with pyrazine-amide-thioether coordination: stabilization of trivalent nickel

机译：具有吡嗪-酰胺-硫醚配位的二价镍和铜配合物的结构和性质：三价镍的稳定化

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摘要

Acyclic pyrazine-2-carboxamide and thioether containing hexadentate ligand 1,4-bis[o-(pyrazine-2-nncarboxamidophenyl)]-1,4-dithiobutane (H(2)bpzctb), in its deprotonated form, has afforded light brown [Ni-II(bpzctb)] (1) (S = 1) and green [Cu-II(bpzctb)] (2) (S = 1/2) complexes. The crystal structures of 1 center dot CH3OH and 2 center dot CH2Cl2 revealed that in these complexes the ligand coordinates in a hexadentate mode, affording examples of distorted octahedral (MN2)-N-II(pyrazine) N'(2)(amide)S-2(thioether) coordination. Each complex exhibits in CH2Cl2 a reversible to quasireversible cyclic voltammetric response, corresponding to the Ni-III/Ni-II (1) and Cu-II/Cu-I (2) redox process. The E-1/2 values reveal that the complexes of bpzctb(2-) are uniformly more anodic by similar to 0.2 V than those of the corresponding complexes with the analogous pyridine ligand, 1,4-bis[o-(pyridine-2-carboxamidophenyl)]1,4-dithiobutane (H(2)bpctb), attesting that compared to pyridine, pyrazine is a better stabilizer of the Ni(II) or Cu(I) state. Coulometric oxidation of the previously reported complex [Ni-II(bpctb)] and 1 generates [Ni-III(bpctb)](+) and [Ni-III(bpzctb)](+) species, which exhibit a LMCT transition in the 470-480 nm region and axial EPR spectra corresponding to a tetragonally elongated octahedral geometry. Complex 2 exhibits EPR spectra characteristic of the d(z)2 ground state.
机译：无环吡嗪-2-羧酰胺和硫醚含有六齿配体1,4-双[o-（吡嗪-2-nncarboxamidophenyl）]-1,4-二硫代丁烷（H（2）bpzctb）呈质子化形式，提供浅棕色[Ni-II（bpzctb）]（1）（S = 1）和绿色[Cu-II（bpzctb）]（2）（S = 1/2）配合物。 1个中心点CH3OH和2个中心点CH2Cl2的晶体结构表明，在这些络合物中，配体以六齿模式配位，提供了扭曲的八面体（MN2）-N-II（吡嗪）N'（2）（酰胺）S的实例-2（硫醚）配合。每个络合物在CH2Cl2中均表现出可逆至准可逆的循环伏安响应，对应于Ni-III / Ni-II（1）和Cu-II / Cu-I（2）氧化还原过程。 E-1 / 2值表明，与具有类似吡啶配体1,4-双[o-（pyridine-2）的相应配合物相比，bpzctb（2-）配合物均匀地阳极化程度接近0.2 V（约0.2 V） -甲酰胺基苯基]]，1,4-二硫丁烷（H（2）bpctb），证明与吡啶相比，吡嗪是Ni（II）或Cu（I）状态的更好的稳定剂。先前报道的配合物[Ni-II（bpctb）]和1的库仑氧化反应产生[Ni-III（bpctb）]（+）和[Ni-III（bpzctb）]（+）物种，它们在LMCT跃迁中表现出470-480 nm区域和轴向EPR光谱对应于四边形伸长的八面体几何形状。配合物2表现出d（z）2基态的EPR光谱特征。

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