Garofalo Nicola, Messa Francesco, Barbanente Alessandra, Fanizzi Francesco Paolo, Salomone Antonio, Margiotta Nicola, Papadia Paride
Department of Biological and Environmental Sciences and Technologies (DiSTeBA), University of Salento, 73100 Lecce, Italy.
Dipartimento di Chimica, Università degli Studi di Bari Aldo Moro, Via E. Orabona 4, 70125 Bari, Italy.
Molecules. 2025 Apr 24;30(9):1890. doi: 10.3390/molecules30091890.
Deep eutectic solvents (DESs) are environmentally friendly solvents formed by combining hydrogen bond donors and acceptors, resulting in a eutectic mixture with a lower melting point than the individual components. While there is extensive research on the electrochemical synthesis of platinum nanoparticles in DESs, to the best of our knowledge, there are no studies on the chemical reactivity of platinum(II) complexes in these systems. This study investigates the simple model reaction between KPtCl and ethylenediamine (), exploring the behaviour in DES environment, to optimize the synthesis of simple cisplatin-like platinum compounds with the potential objective of improving the traditional methods, decreasing the number of steps required for obtaining target compounds and reducing chemical waste. The reactions were performed in two hydrophilic DESs: choline chloride:glycerol 1:2 (glyceline, GL) and choline chloride:ethylene glycol 1:2 (ethaline, EG). The experiments, conducted in a 70% (/) DES and 30% 1:1 HO/DO mixture to allow for direct NMR analysis, revealed that quickly formed [PtCl(en)], which further reacted to produce [Pt(en)]Cl. Reaction products were characterised by 1D (H and Pt{H}) and 2D ([H,C]-HSQC and [H,N]-HSQC) NMR experiments. The discolouration of solutions, due to the consumption of KPtCl, and the precipitation of the purple Magnus salt [Pt(en)][PtCl] occurred over time. The main observed difference between the two solvent mixtures was the slower reactivity in glyceline, due to the much higher viscosity of the solution. Diffusion-ordered spectroscopy (DOSY) indicated lower water mobility in DES mixtures than pure water, with the reaction products closely associated with DES molecules.
深共熔溶剂（DESs）是通过氢键供体和受体结合形成的环境友好型溶剂，形成的共熔混合物熔点低于各组分。虽然关于在深共熔溶剂中电化学合成铂纳米颗粒已有广泛研究，但据我们所知，尚无关于这些体系中铂（II）配合物化学反应性的研究。本研究考察了KPtCl与乙二胺（）之间的简单模型反应，探索在深共熔溶剂环境中的行为，以优化类似顺铂的简单铂化合物的合成，潜在目标是改进传统方法、减少获得目标化合物所需的步骤数量并减少化学废弃物。反应在两种亲水性深共熔溶剂中进行：氯化胆碱:甘油1:2（甘油，GL）和氯化胆碱:乙二醇1:2（乙aline，EG）。实验在70%（/）的深共熔溶剂和30% 1:1 HO/DO混合物中进行，以便进行直接核磁共振分析，结果表明迅速形成了[PtCl(en)]，其进一步反应生成[Pt(en)]Cl。通过一维（H和Pt{H}）和二维（[H,C]-HSQC和[H,N]-HSQC）核磁共振实验对反应产物进行了表征。随着时间推移，由于KPtCl的消耗，溶液变色，紫色的马格努斯盐[Pt(en)][PtCl]沉淀析出。观察到的两种溶剂混合物之间的主要差异是在甘油中的反应活性较慢，这是由于溶液粘度高得多。扩散排序光谱（DOSY）表明，深共熔溶剂混合物中的水流动性低于纯水，反应产物与深共熔溶剂分子紧密相关。
