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首页> 外文期刊>Chemistry: A European journal >Spontaneous reduction of mixed 2,2 '-bipyridine/methylamine/chloro complexes of Pt-IV in water in the presence of light is accompanied by complex isomerization, loss of methylamine, and formation of a strong oxidant, presumably HOCl
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Spontaneous reduction of mixed 2,2 '-bipyridine/methylamine/chloro complexes of Pt-IV in water in the presence of light is accompanied by complex isomerization, loss of methylamine, and formation of a strong oxidant, presumably HOCl

机译：在光的存在下，水中Pt-IV的混合2,2'-联吡啶/甲胺/氯配合物的自发还原反应会伴随有配合物异构化，甲胺的损失以及强氧化剂（大概为HOCl）的形成

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摘要

Three 2,2'-bipyridine (2,2'-bpy) complexes of Pt-IV have been synthesized, characterized by X-ray crystallography, and their solution behavior in D2O studied by H-1 NMR spectroscopic analysis: mer-[PtCl3(2,2'-bpy)(MeNH2)]Cl center dot H2O (4), trans- [PtCl2 (2,2'-bpy)(MeNH2)(2)]Cl (5), and trans-[Pt (2,2'-bpy)(MeNH2)(2)(OH)(2)]Cl-2 (6; MeNH2=methylamine). Complexes 4 and 5 undergo hydrolysis of the Cl- ions, both in the dark and daylight, as evident from a drop in the pH value. Two solvolysis products were detected in the case of 4, which is indicative of species with equatorial and axial OH- groups. ne hydrolysis reaction of 5 implies that an axial Cl- group is replaced by an OH- moiety; in contrast, 6 remains virtually unaffected. Ordinary daylight, in particular irradiation with a 50-W halogen lamp, initially causes ligand-isomerization processes, which are followed by the reduction of 4 and 5 to Ptu species. This reduction of 4 and 5 is accompanied by the formation of hypochlorous acid, as demonstrated qualitatively in the decoloration test of indigo, and loss of MeNH2, which is particularly pronounced in the case of 5. The formation of Pt-II compounds is established on the basis of the J coupling constants of Pt-195 with selected H-1 NMR resonances. The results obtained herein are possibly also relevant to the chemistry of Cl-containing Pt-IV antitumor agents and their reactions with DNA.
机译：合成了三种Pt-IV的2,2'-联吡啶（2,2'-bpy）配合物，通过X射线晶体学表征，并通过H-1 NMR光谱分析研究了它们在D2O中的溶液行为：mer- [PtCl3 （2,2'-bpy）（MeNH2）] Cl中心点H2O（4），反式[PtCl2（2,2'-bpy）（MeNH2）（2）] Cl（5）和反-[Pt（ 2,2′-bpy）（MeNH 2）（2）（OH）（2）] Cl-2（6; MeNH 2 ＝甲胺）。从pH值的下降可以明显看出，配合物4和5在黑暗和白天都经历了Cl-的水解。在4的情况下检测到两种溶剂分解产物，表明具有赤道和轴向OH-基团的物质。 5的水解反应表示轴向的Cl-基被OH-部分取代;相反，有6个实际上没有受到影响。普通日光，特别是用50W卤素灯照射，首先会引起配体异构化过程，然后将4和5还原为Ptu物种。 4和5的这种减少伴随着次氯酸的形成，如靛蓝的脱色试验中定性地证明的，MeNH2的损失在5的情况下尤其明显。Pt-II化合物的形成建立在Pt-195与所选H-1 NMR共振的J耦合常数的基础。本文获得的结果可能还与含Cl的Pt-IV抗肿瘤剂的化学及其与DNA的反应有关。

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