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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Pyridazine-bridged copper(I) complexes of bis-bidentate ligands: tetranuclear [2x2] grid versus dinuclear side-by-side architectures as a function of ligand substituents
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Pyridazine-bridged copper(I) complexes of bis-bidentate ligands: tetranuclear [2x2] grid versus dinuclear side-by-side architectures as a function of ligand substituents

机译：双齿配体的哒嗪桥联铜（I）配合物：四核[2x2]网格与双核并排结构作为配体取代基的函数

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Eight bis-bidentate Schiff-base ligands, derived from 3,6-diformylpyridazine and substituted amino-benzenes, have been prepared. A variety of electron donating/withdrawing and/or sterically demanding/undemanding substituents were employed. Two ligands and five of the six pure copper(I) complexes have been structurally characterised. The sterically unhindered ligand derived from 3,5-difluoroaniline, L-m,L-m-F, was almost completely flat whereas the very sterically hindered ligand derived from trimethylaniline, L-o,L-o,L-p-Me, was severely twisted. The only dinuclear side-by-side complex obtained, [Cu-2(I)(Lo-Ph)(2)](PF6)(2), was of the ligand derived from 2-aminobiphenyl. All five of the other complexes are believed to be [2x2] tetranuclear grid complexes, and this was unequivocally shown to be the case for four of these complexes, [Cu-4(I)(Lp-Me)(4)](PF6)(4), [Cu-4(I)(L-o,L-p-Me)(4)](PF6)(4), [Cu-4(I)(L-m,L-m-F)(4)](PF6)(4) and [Cu-4(I)(L-m,L-m-Cl)(4)](PF6)(4). In all cases the copper(I) centres are substantially distorted from tetrahedral, with the most severe distortion present in the side-by-side complex. In the absence of any special effects, tetracopper(I) [2x2] grid architectures are observed to be the favored outcome for 1:1 reactions of these bis-bidentate ligands with copper(I) ions. Only when the aromaticity of the ligand was extended by employing a phenyl substituent on the phenyl rings, Lo-Ph, did a dicopper(I) side-by-side architecture result. Cyclic voltammetry in acetone revealed that the free ligands did not undergo reduction until potentials below -0.8 V, whereas between three and four reversible one electron reductions were observed, between +0.16 and -0.71 vs. AgCl/Ag, for the tetranuclear copper(I) [2x2] grid complexes. The redox potentials observed for these complexes are highly dependent on the nature of the ligand phenyl ring substituent(s). The side-by-side complex had one irreversible reduction process, E-pc ca.-0.5 V.
机译：制备了8个由3,6-二甲酰基哒嗪和取代的氨基苯衍生的双齿席夫碱配体。使用了各种给电子/吸电子和/或空间上要求/过大的取代基。在结构上已表征了两个配体和六个纯铜（I）络合物中的五个。衍生自3,5-二氟苯胺（L-m，L-m-F）的空间不受阻碍的配体几乎完全平坦，而衍生自三甲基苯胺（L-o，L-o，L-p-Me）的空间非常受阻的配体严重扭曲。获得的唯一双核并排络合物[Cu-2（I）（Lo-Ph）（2）]（PF6）（2）是衍生自2-氨基联苯的配体。其他所有五个复合物都被认为是[2x2]四核网格复合物，并且明确地证明了其中四个复合物[Cu-4（I）（Lp-Me）（4）]（PF6）的情况。 ）（4），[Cu-4（I）（Lo，Lp-Me）（4）]（PF6）（4），[Cu-4（I）（Lm，LmF）（4）]（PF6）（ 4）和[Cu-4（I）（Lm，Lm-Cl）（4）]（PF6）（4）。在所有情况下，铜（I）中心都基本从四面体变形，并排复合物中存在最严重的变形。在没有任何特殊影响的情况下，对于这些双双齿配体与铜（I）离子1：1的反应，发现tetracopper（I）[2x2]网格结构是受青睐的结果。仅当通过在苯环上使用苯基取代基（Lo-Ph）扩展配体的芳香性时，才能形成dicopper（I）并排结构。丙酮中的循环伏安法表明，直到-0.8 V以下电势，游离配体才发生还原，而四核铜（I ）[2x2]网格复合体。对于这些络合物观察到的氧化还原电势高度依赖于配体苯环取代基的性质。并排的络合物具有一个不可逆的还原过程，E-pc约为-0.5V。

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