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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Crucial role of Cu-S bonding for structural changes accompanying the reversible Cu-I/Cu-II transition in an unrestrained Cu(N boolean AND S)(2) coordination arrangement. An experimental and DFT study
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Crucial role of Cu-S bonding for structural changes accompanying the reversible Cu-I/Cu-II transition in an unrestrained Cu(N boolean AND S)(2) coordination arrangement. An experimental and DFT study

机译：Cu-S键对于伴随无约束的Cu（N布尔AND S）（2）配位结构中可逆的Cu-I / Cu-II转变伴随的结构变化的关键作用。实验和DFT研究

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The structure of reversibly oxidizable [Cu(mmb)(2)](BF4) with 1-methyl-2-(methylthiomethyl)-1H-benzimidazole (mmb) as bidentate N,S-donor ligand has been determined and compared with that of the copper(II) species [Cu(mmb)(2)(eta (1)-ClO4)](ClO4). In the complex ions of the equilibrium [Cu-I(mmb)(2)](+) + ClO4- reversible arrow e(-) + [Cu-II(mmb)(2)(eta (1)-ClO4)](+) the almost linear N-Cu-N backbone is invariant whereas the bonds to the thioether sulfur centers and especially the changing S-Cu-S angle (145.18(5)degrees for the Cu-II Species, 109.33(3)degrees for the Cu-I form) reflect the metal oxidation state. In contrast to the perchlorate coordinating copper(II) species, [Cu-I(mmb)(2)](BF4) contains a cation with a very large vacant site at the metal center, resulting in elliptical channels within the crystal. DFT calculations on [Cu-I(mb)(2)](+), [Cu-II(mb)(2)](2+), and [Cu-II(mb)(2)(OClO3)](+) with mb = 2-methylthiomethyl-1H-benzimidazole confirm the essential role of the metal-sulfur bonds in responding to the reversible Cu-I/II electron transfer process, even in the absence of electronically stronger interacting thiolate sulfur centers or sophisticated oligodentate ligands. [References: 25]
机译：确定了以1-甲基-2-（甲硫甲基）-1H-苯并咪唑（mmb）为双齿N，S-施主配体可逆氧化的[Cu（mmb）（2）]（BF4）的结构，并将其与铜（II）物种[Cu（mmb）（2）（eta（1）-ClO4）]（ClO4）。在平衡态的复合离子中[Cu-I（mmb）（2）]（+）+ ClO4-可逆箭头e（-）+ [Cu-II（mmb）（2）（eta（1）-ClO4）] （+）几乎线性的N-Cu-N主链是不变的，而与硫醚硫中心的键尤其是不断变化的S-Cu-S角（Cu-II物种为145.18（5）度，109.33（3）度对于Cu-I形式）反映金属的氧化态。与高氯酸盐配位的铜（II）物种相反，[Cu-I（mmb）（2）]（BF4）包含在金属中心具有非常大的空位的阳离子，从而在晶体内形成椭圆形通道。 [Cu-I（mb）（2）]（+），[Cu-II（mb）（2）]（2+）和[Cu-II（mb）（2）（OClO3）]的DFT计算+）与mb = 2-甲基硫代甲基-1H-苯并咪唑证实了金属-硫键在响应可逆Cu-I / II电子转移过程中的重要作用，即使在没有电子上相互作用更强的硫醇盐硫中心或复杂的低聚体的情况下配体。 [参考：25]

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