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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >The coordination of perrhenate and pertechnetate to thorium(IV) in the presence of phosphine oxide or phosphate ligands
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The coordination of perrhenate and pertechnetate to thorium(IV) in the presence of phosphine oxide or phosphate ligands

机译：在氧化膦或磷酸盐配体存在下高r酸盐和高tech酸盐与th（IV）的配位

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A series of thorium(IV) perrhenato- and pertechnetato-complexes with P = O donor ligands have been prepared and characterised both in the solid state and in solution. Isostructural complexes of general formula [Th(MO4)(4)(L)(4)], where M = Re or Tc and L = triethylphosphate (TEP) (2 and 7), tri-iso-butylphosphate (TiBP) (3 and 8) and tri-n-butylphosphine oxide (TBPO) (4 and 9) have been prepared from the novel starting materials [Th(ReO4)(4)]center dot 4H(2)O (1) and [Th(TcO4)(4)]center dot 4H(2)O (6). The reaction of 1 or 6 with triphenylphosphine oxide (TPPO) in MeOH has also led to the synthesis of [Th(MO4)(3)(TPPO)(3)(OCH3)(HOCH3)] (M = Re (5) or Tc (10)). While the structural characterisation of 4 and 9 has been previously described, we report for the first time the structural characterisation of 2 and 5, with a partial structural refinement of 3. Vibrational spectroscopic analysis confirms that the Tc complexes not characterised by single crystal X-ray diffraction are indeed isostructural with the perrhenate complexes with the same P = O donor ligand. In all cases, monodentate coordination of the Group 7 tetraoxo anion is observed. P-31 NMR spectroscopy indicates that in all the phosphine oxide-based complexes there is one dominant solution species. For the phosphate based systems, the presence of pertechnetate appears to inhibit P = O donor ligand complexation in solution, whereas a significant proportion of each phosphate remains coordinated to Th-IV when perrhenate is present as the counter ligand. These results give some indication as to the mechanism of pertechnetate co-extraction with tetravalent cations in the presence of tri-n-butyl phosphate in the Plutonium and Uranium Recovery by Extraction (PUREX) process.
机译：已经制备了一系列具有P = O供体配体的per（Ⅳ）高r和高tech络合物，并在固态和溶液中进行了表征。通式[Th（MO4）（4）（L）（4）]的同构配合物，其中M = Re或Tc，L =磷酸三乙酯（TEP）（2和7），磷酸三异丁酯（TiBP）（3和8）和三正丁基氧化膦（TBPO）（4和9）已从新型原料[Th（ReO4）（4）]中心点4H（2）O（1）和[Th（TcO4 ）（4）]中心点4H（2）O（6）。 1或6与三苯基氧化膦（TPPO）在MeOH中的反应还导致[Th（MO4）（3）（TPPO）（3）（OCH3）（HOCH3）]的合成（M = Re（5）或Tc（10））。虽然先前已经描述了4和9的结构特征，但我们还是首次报道了2和5的结构特征，其中部分结构进行了3改进。振动光谱分析证实Tc络合物没有以单晶X-射线衍射的确是高per酸盐配合物具有相同的P = O供体配体的同构。在所有情况下，均观察到第7族四氧阴离子的单齿配位。 P-31 NMR光谱表明，在所有基于氧化膦的配合物中，都有一种主要的溶液种类。对于基于磷酸盐的系统，高tech酸酯的存在似乎抑制了溶液中P = O供体配体的络合，而当高r酸酯作为对位配体存在时，每种磷酸盐的很大一部分仍与Th-IV保持配位。这些结果表明在phosphate和铀回收萃取（PUREX）过程中在磷酸三正丁酯存在下高of酸酯与四价阳离子共萃取的机理。

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