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首页> 外文期刊>RSC Advances >Steric and electronic control over the structural diversity of N-(n-pyridinyl) diphenylphosphinic amides (n = 2 and 4) as difunctional ligands in triphenyltin(IV) adducts
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Steric and electronic control over the structural diversity of N-(n-pyridinyl) diphenylphosphinic amides (n = 2 and 4) as difunctional ligands in triphenyltin(IV) adducts

机译：立体和电子控制N-（n-吡啶基）二苯基次膦酰胺（n = 2和4）作为三苯基锡（IV）加合物中双官能配体的结构多样性

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摘要

Two triphenyltin(IV) adducts of difunctional ligands, N-(n-pyridinyl) diphenylphosphinic amide (n = 2 and 4), have been synthesized and characterized by H-1, P-31, Sn-119 NMR and IR spectroscopy. The spectroscopic properties of the complexes were compared with those of corresponding ligands. The crystal structures of the complexes were determined by X-ray crystallography, which reveals a trigonal bipyramidal geometry surrounding the tin(IV). Both of the ligands function in an ambidentate mode, ligating through either the O or N atom. The experimental and theoretical (DFT) studies show that the Sn(IV) interacts more strongly with the N-pyridine atom than the P=O functional group. Furthermore, DFT calculations, at the B3LYP level, have been carried out to determine the deeper reasons for the adopted bonding mode in the complexes. The influence of the ligand structure on the coordination behaviour and the contribution of hydrogen bonding to the stability of the resulting complexes were elucidated. The results indicate that the intermolecular hydrogen bonds have an important role in the molecular structures and supramolecular associations of the organotin(IV) compounds.
机译：合成了两个双官能配体的三苯基锡（IV）加合物，N-（正吡啶基）二苯基次膦酰胺（n = 2和4），并通过H-1，P-31，Sn-119 NMR和IR进行了表征。将配合物的光谱性质与相应配体的光谱性质进行比较。配合物的晶体结构是通过X射线晶体学确定的，它揭示了锡（IV）周围的三角双锥体几何形状。两个配体均以双键模式起作用，通过O或N原子连接。实验和理论（DFT）研究表明，Sn（IV）与N-吡啶原子的相互作用比P = O官能团的相互作用更强。此外，已经在B3LYP级别上进行了DFT计算，以确定在复合物中采用键合模式的更深层原因。阐明了配体结构对配位行为的影响以及氢键对所得配合物稳定性的影响。结果表明，分子间氢键在有机锡（IV）化合物的分子结构和超分子缔合中具有重要作用。

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