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首页> 外文期刊>Chemistry: A European journal >Synthesis, structure, and reactivity of a dimeric zinc(I) Compound stabilized by a sterically demanding diiminophosphinate ligand
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Synthesis, structure, and reactivity of a dimeric zinc(I) Compound stabilized by a sterically demanding diiminophosphinate ligand

机译：通过空间需求的二亚氨基次膦酸酯配体稳定的二聚锌（I）化合物的合成，结构和反应活性

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摘要

The new sterically demanding aminoiminophosphorane Ph_2P(=NDip) (NHDip) (Dip=C_6H_3-2,6-iPr_2; LH, 1) has been prepared as a precursor to the potassium complex [LK] (2) and a series of heteroleptic zinc(II) complexes, namely [(LZnBr)_2] (3), [LZnMe] (4), [LZnEt] (5), and [(LZnI)_2] (6). The products have been obtained either through a salt metathesis route by using complex 2 and ZnBr_2 to give compound 3, through a direct reaction of ligand precursor 1 and ZnR _2 (R=Me or Et) yielding complexes 4 or 5, respectively, or through iodination of complexes 4 or 5 by using I2 to afford compound 6. Reduction of the heteroleptic zinc(II) halide complexes 3 or 6 by using a dimeric magnesium(I) compound as a selective, stoichiometric, and soluble reducing agent afforded the new zinc(I) dimer [(LZn)_2] (7) in good yield. Compounds 1-7 were crystallographically and spectroscopically characterized and the coordination behavior of the diiminophosphinate ligand has been investigated and compared with related CN-based ligands. An initial reactivity study has been carried out on [(LZn)_2] (7) by using small-scale reactions and the oxidative addition of small alkyl halides across the Zn-Zn bond has been found to generate equimolar amounts of the alkyl complexes 4 or 5 and the halide complexes 3 or 6, respectively.
机译：新的空间需求氨基亚氨基正膦Ph_2P（= NDip）（NHDip）（Dip = C_6H_3-2,6-iPr_2; LH，1）已制备为钾络合物[LK]（2）和一系列杂合锌的前体（II）配合物，即[（LZnBr）_2]（3），[LZnMe]（4），[LZnEt]（5）和[（LZnI）_2]（6）。通过配合物2和ZnBr_2通过配位体前体1和ZnR _2（R = Me或Et）直接反应生成配合物4或5的盐易位反应，通过盐复分解途径获得了产物。通过使用I2对配合物4或5进行碘化，得到化合物6。通过使用二聚镁（I）化合物作为选择性，化学计量和可溶性还原剂还原杂配锌（II）卤化物配合物3或6，得到了新的锌。 （I）二聚体[（LZn）_2]（7），收率良好。对化合物1-7进行了晶体学和光谱学表征，研究了二亚氨基次膦酸酯配体的配位行为，并将其与相关的基于CN的配体进行了比较。通过使用小规模反应，已对[（LZn）_2]（7）进行了初步反应性研究，发现小分子卤化物通过Zn-Zn键的氧化加成反应生成了等摩尔量的烷基络合物4或5与卤化物配合物3或6。

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