Fundamental coordination chemistry of Mo(VI) at its macroconcentrations in solvent extraction systems is of great importance for industrial processes that require the purification or recovery of large concentrations of Mo. The coordination of Mo(VI) in tri-n-butyl phosphate (TBP) from solutions of hydrochloric acid and up to 0.3 M Mo was investigated using UV, FTIR, and ³¹P NMR spectroscopies, as well as EXAFS. From these techniques we resolved near-neighbor atoms, speciation, structural information on the coordination environment, and thermodynamic parameters affiliated with the solvent extraction of Mo(VI) and HCl. The solvated extracted form of Mo(VI) as MoO₂Cl₂·2TBP was identified. High extraction yield of Mo at >5 M HCl concentration is driven by replacing HCl in the organic phase by Mo. The existence of additional organic Mo adducts is also discussed with the aid of density functional theory, however no evidence of dimeric or polymeric Mo species was found to be present in TBP.

中文翻译：

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磷酸三丁酯氯化物体系中的钼（VI）配位

在其在溶剂萃取系统macroconcentrations沫的基本配位化学（VI）是用于需要在三-纯化或高浓度的钼（VI）的Mo中的至少协调的回收工业过程非常重要Ñ丁基磷酸酯（TBP使用UV，FTIR和³¹ P NMR光谱仪以及EXAFS研究了盐酸和最高0.3 M Mo溶液中的）。从这些技术中，我们解析了近邻原子，物种，配位环境的结构信息以及与Mo（VI）和HCl溶剂萃取有关的热力学参数。Mo（VI）的溶剂化提取形式为MoO ₂ Cl ₂·确定了2TBP。通过用Mo代替有机相中的HCl，可以在> 5 M HCl浓度下获得高的Mo提取率。还借助密度泛函理论讨论了其他有机Mo加合物的存在，但是没有二聚或聚合Mo物种的证据。被发现存在于TBP中。