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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Investigation of the extraction complexes of palladium(ii) with novel thiodiglycolamide and dithiodiglycolamide ligands by EXAFS and computational methods
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Investigation of the extraction complexes of palladium(ii) with novel thiodiglycolamide and dithiodiglycolamide ligands by EXAFS and computational methods

机译：用EXAFS和计算方法研究新型硫代二甘醇酰胺和二硫代二甘醇酰胺配体提取钯（ii）的配合物

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摘要

The structure of the extraction complexes of palladium(ii) with novel ligands, namely, N,N,N′,N′-tetra-(2-ethylhexyl) thiodiglycolamide (T(2EH)TDGA) and N,N,N′,N′-tetra-(2-ethylhexyl) dithiodiglycolamide (DTDGA), have been determined by extended X-ray absorption fine structure spectroscopy (EXAFS). The interpretation of the EXAFS data is well supported by theoretical calculations of the complex geometry based on density functional theory (DFT). T(2EH)TDGA, having one thioetheric 'S' atom, forms a square planar complex with the Pd(ii) ion, exhibiting 2: 1 stoichiometry with one sulphur atom and one carbonyl oxygen atom from each T(2EH)TDGA molecule interacting with Pd(ii) at distances of 2.24 and 2.04 ?, respectively. On the other hand, DTDGA, having two 'S' atoms in addition to two carbonyl groups, forms a square planar complex with Pd(ii), exhibiting 1: 1 stoichiometry, wherein both the sulphur atoms and the carbonyl oxygen of DTDGA interact with Pd(ii) at distances of 2.29 and 2.05 ?, respectively. The slight distortion from the perfect square planar geometry could be attributed to the steric hindrance imposed by the bulky alkyl group of the amidic moieties. DFT calculations for the Pd-ligand complexes show that the Pd(ii)-DTDGA complex with 1: 1 stoichiometry is energetically more stable than the Pd(ii)-T(2EH)TDGA complex with 1: 2 stoichiometry. Among the two possible Pd(ii)-T(2EH)TDGA complex geometries, the cis configuration appears more favorable. The methodology of fitting the EXAFS data has been validated by fitting the EXAFS data of a Pd(ii)-aquo complex which showed square planar geometry with two axial water molecules constituting the secondary hydration sphere.
机译：钯（ii）与新型配体即N，N，N'，N'-四-（2-乙基己基）硫代二甘醇酰胺（T（2EH）TDGA）和N，N，N'的萃取配合物的结构， N'-四-（2-乙基己基）二硫二甘醇酰胺（DTDGA）已通过扩展X射线吸收精细结构光谱法（EXAFS）确定。基于密度泛函理论（DFT）的复杂几何结构的理论计算很好地支持了EXAFS数据的解释。具有一个硫醚'S'原子的T（2EH）TDGA与Pd（ii）离子形成方形平面络合物，化学计量比为2：1，每个T（2EH）TDGA分子相互作用的一个硫原子和一个羰基氧原子Pd（ii）的距离分别为2.24和2.04?。另一方面，除两个羰基外还具有两个'S'原子的DTDGA与Pd（ii）形成方形平面络合物，化学计量比为1：1，其中DTDGA的硫原子和羰基氧都与Pd（ii）的距离分别为2.29和2.05?。理想的正方形平面几何形状的轻微变形可归因于酰胺部分的庞大烷基所施加的位阻。对Pd-配体配合物的DFT计算表明，化学计量比为1：1的Pd（ii）-DTDGA配合物比化学计量比为1：2的Pd（ii）-T（2EH）TDGA配合物在能量上更稳定。在两种可能的Pd（ii）-T（2EH）TDGA复杂几何结构中，顺式构型似乎更有利。拟合EXAFS数据的方法已通过拟合Pd（ii）-aquo复合物的EXAFS数据进行了验证，该Pd（ii）-aquo络合物显示方形平面几何形状，并且两个轴向水分子构成了次级水化球。

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