In the sense of green chemistry and green engineering, it is of great significance to obtain a simple and practicable quantum chemistry approach for extractant prescreening toward platinum group metals (PGMs). In this work, we assessed the performances of five functionals (B3LYP, CAM-B3LYP, M06, M06-2X, and ωB97X-D) and two solvation models (the SMD and SMD-GIL models) for identifying the coordination atoms of possible multisite extractants by ESP–ALIE analysis (i.e., a combination of electrostatic potential analysis and average local ionization energy analysis). First, for the test sets consisting of two neutral extractants and two ionic liquid extractants in ionic liquid solvents for Pd(II) extraction, the reliability of ESP–ALIE analysis for complexation site identification was validated by the crystal evidences. Subsequently, to provide data for the predictive ability of ESP–ALIE analysis, variable influence factors (e.g., extractant concentration, HCl concentration, and Cl^– concentration) and mechanism on the Pt(IV) extraction with a neutral extractant in ionic liquid diluents were explored. The extracted complex Pt(BMImT)₂Cl₄, whose single-crystal data were first reported herein, validated the theoretical forecast from the ESP–ALIE point of view. Overall, ESP–ALIE analysis is a promising quantum chemistry tool for identifying the coordination atoms of possible multisite extractants toward PGMs.

中文翻译：

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ESP–ALIE分析作为识别可能的多部位萃取剂配位原子的理论工具：验证和预测

从绿色化学和绿色工程的意义上讲，获得一种简单可行的量子化学方法对铂族金属（PGM）进行萃取剂预筛选具有重要意义。在这项工作中，我们评估了五个功能（B3LYP，CAM-B3LYP，M06，M06-2X和ωB97X-D）和两个溶剂化模型（SMD和SMD-GIL模型）的性能，以识别可能的多位点配位原子ESP-ALIE分析（即静电势分析和平均局部电离能分析的组合）提取萃取剂。首先，对于由两种中性萃取剂和两种离子液体萃取剂组成的测试溶液，在用于Pd（II）萃取的离子液体溶剂中，晶体证据证实了ESP–ALIE分析用于络合位点鉴定的可靠性。后来，^–浓度）以及在离子液体稀释剂中用中性萃取剂萃取Pt（IV）的机理。提取的复合物Pt（BMImT）₂ Cl ₄，其单晶数据首次在此报道，从ESP–ALIE的角度验证了理论预测。总体而言，ESP-ALIE分析是一种有前途的量子化学工具，可用于识别可能的多位萃取剂对PGM的配位原子。