Zazulya Alexei, Berdyugin Semen, Tkachev Sergey, Lagunova Varvara, Sheven Dmitriy, Abramov Pavel, Glebov Evgeni, Vasilchenko Danila
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Science, 630090 Novosibirsk, Russia.
Novosibirsk State University, 630090Novosibirsk, Russia.
Inorg Chem. 2025 Feb 10;64(5):2336-2347. doi: 10.1021/acs.inorgchem.4c04536. Epub 2025 Jan 28.
The photoinduced reaction of [Pt(NO)] with pyridine or its derivatives (L) was found to result in the formation of PtL salts in high yield. This transformation was successfully probed for methyl- and carboxyethyl-substituted pyridines, and the corresponding PtL salts were isolated and fully characterized using single-crystal X-ray diffraction (SCXRD). Anation of the [Pt(py)] cationic complex with N was studied by H NMR spectroscopy in aqueous and water/dimethyl sulfoxide solutions of Pt(py). A mixture of cis- and trans-[Pt(py)(N)] complexes was determined as the final product of this interaction with the domination of the trans-isomer (cis to trans ratio is about 1:8) due to its preferable formation from the transient [Pt(py)(N)] cationic complex. The difference observed for the experimentally determined activation parameters of trans- and cis-paths of anation was supported by DFT calculations. Finally, the new three-stage Ag-free synthetic procedure for the preparation of the trans,trans-[Pt(py)(N)(OH)] prodrug (potential agent for the photodynamic anticancer therapy) was found using (i) light-induced formation of Pt(py) from (BuN)[Pt(NO)] followed by (ii) anation of [Pt(py)] with azide and (iii) accomplished by oxidation of the resulting mixture of cis- and trans-[Pt(py)(N)] with HO. Efficient separation of cis,trans-[Pt(py)(OH)(N)] and trans,trans-[Pt(py)(N)(OH)] produced at the last stage was achieved by simple recrystallization from water.
发现[Pt(NO)]与吡啶或其衍生物（L）的光诱导反应能高产率地生成PtL盐。该转化过程已成功应用于甲基和羧乙基取代的吡啶，并通过单晶X射线衍射（SCXRD）对相应的PtL盐进行了分离和全面表征。在Pt(py)的水溶液和水/二甲基亚砜溶液中，通过¹H NMR光谱研究了[Pt(py)]阳离子配合物与叠氮化物的配位反应。顺式和反式-[Pt(py)₂(N₃)]配合物的混合物被确定为该相互作用的最终产物，由于其更倾向于从瞬态[Pt(py)₂(N₃)]阳离子配合物形成，反式异构体占主导（顺式与反式比例约为1:8）。密度泛函理论（DFT）计算支持了实验测定的反式和顺式配位路径活化参数的差异。最后，发现了一种新的无银三步合成方法来制备反式、反式-[Pt(py)₂(N₃)(OH)]前药（光动力抗癌治疗的潜在药物），具体步骤为：(i) 光诱导使 (Bu₄N)[Pt(NO)₂]生成Pt(py)₂，接着 (ii) 用叠氮化物使[Pt(py)₂]进行配位，以及 (iii) 通过用H₂O₂氧化所得的顺式和反式-[Pt(py)₂(N₃)]混合物来完成。通过简单的水重结晶实现了最后一步生成的顺式、反式-[Pt(py)₂(OH)(N₃)]和反式、反式-[Pt(py)₂(N₃)(OH)]的有效分离。
