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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Dehydrogenation of amines in aryl-amine functionalized pincer-like nitrogen-donor redox non-innocent ligands via ligand reduction on a Ni(II) template
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Dehydrogenation of amines in aryl-amine functionalized pincer-like nitrogen-donor redox non-innocent ligands via ligand reduction on a Ni(II) template

机译：通过配体还原在Ni（II）模板上通过配体还原脱氢芳基胺官能化钳样氮气供体氧化还原非无辜配体的脱氢

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摘要

We have synthesized a series of new redox non-innocent azo aromatic pincer-like ligands: 2-(phenylazo)-6-(arylaminomethyl)pyridine (HLa-c: HLa = 2-(phenylazo)-6-(2,6-diisopropylphenylaminomethyl)pyridine, HLb = 2-(phenylazo)-6-(2,6-dimethylphenylaminomethyl)pyridine, and HLc = 2-(phenylazo)-6-(phenylaminomethyl)pyridine), in which one side arm is an arylaminomethyl moiety and the other arm is a 2-phenylazo moiety. Nickel(II) complexes, 1-3, of these ligands HLa-c were synthesized in good yield (approximately 70%) by the reaction of ligands:(NiCl(2)6H(2)O) in a 1:1 molar ratio in methanol. The amine donor in each of the ligands HLa-c binds to the Ni(II) centre without deprotonation. In the solid state, complex 3 is a dimer; in solution it exists as monomer 3a. The reduction of acetonitrile solutions of each of the complexes 1, 2 and 3a, separately, with cobaltocene (1 equivalent), followed by exposure of the solution to air, resulted in the formation of new complexes 7, 8 and 9, respectively. Novel free ligands L-x and L-y have also been isolated, in addition to complexes 7 and 8, from the reaction of complexes 1 and 2, respectively. Complexes 7-9 and free ligands L-x and L-y have been formed via a dehydrogenation reaction of the arylaminomethyl side arm. The mechanism of the reaction was thoroughly investigated using a series of studies, including cyclic voltammetry, EPR, and UV-Vis spectral studies and density functional theory (DFT) calculations. The results of these studies suggest a mechanism initiated by ligand reduction followed by dioxygen activation. A Cl-/I- scrambling experiment revealed that the dissociation of the chloride ligand(s) was associated with the one-electron reduction of the ligand (azo moiety) in each of the complexes 1, 2 and 3a. The dissociated chloride ligand(s) were reassociated with the metal following the dehydrogenation reaction to yield the final products. All of the newly synthesized compounds were fully characterized using a variety of physicochemical techniques. Single-crystal X-ray structures of the representative compounds were determined to confirm the identities of the synthesized molecules.
机译：我们已经合成了一系列新的氧化还原非无辜偶氮芳香族钳样配体：2-（苯氮杂）-6-（芳基氨基甲基）吡啶（HLA-C：HLA = 2-（苯氮杂）-6-（2,6-二异丙基苯胺甲基）吡啶，HLB = 2-（苯氮杂）-6-（2,6-二甲基苯基氨基甲基）吡啶，以及HLC = 2-（苯基苯基）-6-（苯基氨基甲基）吡啶），其中一个侧臂是芳基氨基甲基部分和另一只臂是2-苯基氮杂部分。通过配体的反应（NiCl（2）6H（2）O）为1：1摩尔比的反应，将这些配体HLA-C的镍络合物（约70％）合成。1：1的摩尔比在甲醇中。在每个配体中的胺供体HLA-C与Ni（II）中心结合而不进行去质子化。在固态中，复合物3是二聚体;在溶液中，它存在为单体3a。将各自的络合物1,2和3a中的每一个的乙腈溶液的降低分开，用钴茂（1当量），然后暴露于空气中的溶液，导致形成新的复合物7,8和9。除了复合物1和2的复合物7和8之外，还分离了新的游离配体L-X和L-Y。通过芳族氨基甲基侧臂的脱氢反应形成复合物7-9和游离配体L-X和L-Y.使用一系列研究彻底研究了反应的机制，包括循环伏安法，EPR和UV-Vis光谱研究和密度泛函理论（DFT）计算。这些研究的结果表明，通过配体还原后的机制随之而来引发二恶英激活。 CL- / I-丙粘合实验显示，氯化物配体的解离与配合物1,2和3A中的每个配体（偶氮部分）的单电子还原有关。在脱氢反应后用金属重新分配解离氯化物配体，得到最终产物。所有新合成的化合物都使用各种物理化学技术完全表征。确定代表性化合物的单晶X射线结构以确认合成分子的标识。

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