Pd(ii) and Ni(ii) complexes featuring a 'phosphasalen' ligand: Synthesis and DFT study

Cao T.-P.-A.; Labouille S.; Auffrant A.; Jean Y.; Le Goff X.F.; Le Floch P.

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Pd(ii) and Ni(ii) complexes featuring a 'phosphasalen' ligand: Synthesis and DFT study

机译：具有“ phosphasalen”配体的Pd（ii）和Ni（ii）配合物：合成和DFT研究

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A phosphorus analog of salen ligands featuring iminophosphorane functionalities in place of the imine groups was synthesised in 2 steps from o-diphenylphosphinophenol via the preparation of the corresponding bis-aminophosphonium salt. This novel tetradentate ligand (1), which we named phosphasalen, was coordinated to Pd(ii) and Ni(ii) metal centres affording complexes 6 and 7 respectively, which were characterised by multinuclear NMR, elemental and X-ray diffraction analyses. Both neutral complexes adopt a nearly square-planar geometry around the metal with coordination of all iminophosphorane and phenolate moieties. The electronic properties of these new complexes were investigated by cyclic voltammetry and comparison with known salens was made when possible. Moreover, the particular behaviour of the phosphasalen nickel complex 7 was further investigated through magnetic moment measurements and a DFT study.

机译：通过制备相应的双氨基amino盐，由邻二苯基膦基苯酚分两步合成了具有亚氨基膦酸酯官能团的亚胺基取代分子的萨伦配体的磷类似物。我们将这种新的四齿配体（1）命名为phosphasalen，与Pd（ii）和Ni（ii）金属中心配位，分别提供配合物6和7，并通过多核NMR，元素和X射线衍射分析对其进行表征。两种中性络合物在金属周围都采用近似正方形平面的几何形状，并与所有亚氨基磷烷和酚盐部分配合。通过循环伏安法研究了这些新配合物的电子性质，并在可能的情况下与已知的塞伦进行了比较。此外，通过磁矩测量和DFT研究进一步研究了磷asalen镍配合物7的特殊行为。

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《Dalton transactions: An international journal of inorganic chemistry》 |2011年第39期|共9页
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Cao T.-P.-A.; Labouille S.; Auffrant A.; Jean Y.; Le Goff X.F.; Le Floch P.;
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Pd(ii) and Ni(ii) complexes featuring a 'phosphasalen' ligand: Synthesis and DFT study

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