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Triorganotin(IV) derivatives with semirigid heteroditopic hydroxo‐carboxylato ligands: Synthesis, characterization, and cytotoxic properties
Applied Organometallic Chemistry ( IF 3.7 ) Pub Date : 2020-11-10 , DOI: 10.1002/aoc.6080 Tushar S. Basu Baul 1 , Maheswara Rao Addepalli 1 , Andrew Duthie 2 , Priya Singh 3 , Biplob Koch 3 , Hans Gildenast 4 , Ulli Englert 4 , Irán Rojas‐León 5 , Herbert Höpfl 5
Applied Organometallic Chemistry ( IF 3.7 ) Pub Date : 2020-11-10 , DOI: 10.1002/aoc.6080 Tushar S. Basu Baul 1 , Maheswara Rao Addepalli 1 , Andrew Duthie 2 , Priya Singh 3 , Biplob Koch 3 , Hans Gildenast 4 , Ulli Englert 4 , Irán Rojas‐León 5 , Herbert Höpfl 5
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Three organic hydroxy‐carboxylic acids separated by a semirigid aromatic diaza scaffold and carrying alkyl groups of different steric hindrance (H′HL1, cyclopropyl; H′HL2, cyclohexyl; H′HL3, adamantyl) were employed as pro‐ligands. Their reaction with suitable triorganotin precursors leads to 10 complexes of compositions: [Me3Sn(HL1)]n·0.5nC6H5CH3 1, [Et3Sn(HL1)]n 2, [nBu3Sn(HL1)]n 3, [Ph3Sn(HL1)]n 4, [Me3Sn(HL2)]2·2CH2Cl2 5, [Et3Sn(HL2)]2 6, {[nBu3Sn(HL2)][nBu3Sn(HL2)(H2O)]} 7, [Ph3Sn(HL2)]n·nC2H5OH 8, [nBu3Sn(HL3)]n 9, and [Ph3Sn(HL3)]n 10. The solid‐state structures of 1–10 were deduced from single‐crystal X‐ray diffraction studies along with two of the pro‐ligands: H′HL1 and H′HL2. In the solid state, four different extended structure types were observed. In compounds 1–3 with aliphatic substituents at the tin atoms and a small substituent at the ligand backbone (cyclopropyl), 1D coordination polymers based on carboxylate bridging were observed, whereas compounds 4 and 8–10 with large substituents attached to the metal and the ligand (cyclohexyl and adamantyl) were 1D coordination polymers based on heteroditopic binding of the ligands. Albeit having essentially the same ligand conformation, the compounds having smaller substituents at the tin atoms (5, R = Me; 6, R = Et) comprise 24‐membered macrocyclic ring structures. In 7, water molecules are coordinated to half the tin atoms, giving dinuclear fragments {[HL2][nBu3Sn][HL2][nBu3Sn(H2O)]}, which are linked through OwH···Osal hydrogen bonds into 1D hydrogen‐bonded tapes. In solution, the tin atoms in 1–10 are coordinated to a single monoanionic [HL1–3]− ligand molecule utilizing anisobidentate coordination with the carboxylate group, as revealed from 119Sn nuclear magnetic resonance spectral results. The antiproliferative activity of the tri‐n‐butyl and triphenyltin compounds 3, 4, and 7–10 was evaluated against the cervical cancer cells (HeLa) and normal kidney cells (HEK) using the 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay. Of these, the adamantyl‐substituted tin complexes 9 and 10 present increased activity with IC50 values of 0.51 ± 0.01 and 0.41 ± 0.03 (μM) and good selectivity. The cell death mechanism was identified as apoptosis based on dual staining with fluorescent dyes (Hoechst 33342/propidium iodide and acridine orange/ethidium bromide) and might be related to reactive oxygen species.
中文翻译：
具有半刚性异位羟基羰基羧酸配体的Triorganotin（IV）衍生物：合成，表征和细胞毒性
使用由半刚性芳族重氮骨架分隔并带有不同空间位阻的烷基（H'HL 1，环丙基；H'HL 2，环己基；H'HL 3，金刚烷基）隔开的三种有机羟基羧酸。它们与合适的三有机锡前体的反应产生10种组成的复合物：[Me 3 Sn（HL 1）] n ·0.5nC 6 H 5 CH 3 1，[Et 3 Sn（HL 1）] n 2，[ n Bu 3 Sn （HL 1）]n 3，[Ph 3 Sn（HL 1）] n 4，[Me 3 Sn（HL 2）] 2 ·2CH 2 Cl 2 5，[Et 3 Sn（HL 2）] 2 6，{[ n Bu 3 Sn （HL 2）] [ n Bu 3 Sn（HL 2）（H 2 O）]} 7，[Ph 3 Sn（HL 2）] n ·nC 2 H 5 OH 8，[n Bu 3 Sn（HL 3）] n 9和[Ph 3 Sn（HL 3）] n 10。1 – 10的固态结构是从单晶X射线衍射研究以及两个前配体：H'HL 1和H'HL 2推导出来的。在固态下，观察到四种不同的扩展结构类型。在化合物1 - 3与锡原子和配体主链（环丙基）小取代基脂族取代基中，观察到基于羧酸类桥接1D配位聚合物，而化合物4和8 - 10与附着在金属和配体（环己基和金刚烷基）的取代基大都是基于heteroditopic的配体的结合1D配位聚合物。尽管具有基本相同的配体构象，但在锡原子上具有较小取代基的化合物（5，R = Me；6，R = Et）包含24元大环结构。在7中，水分子与锡原子的一半配位，产生双核碎片{[HL 2 ] [ n Bu 3 Sn] [HL 2 ] [ n Bu 3 Sn（H 2 O）]}，它们通过O连接瓦特 ħ···ö SAL氢键成1D氢键磁带。在溶液中，在锡原子1 - 10被协调到单个单阴离子[HL 1-3 ] -配体分子利用与羧酸酯基anisobidentate协调，如从显示119分的Sn核磁共振光谱的结果。三元的抗增殖活性Ñ丁基，三苯基锡化合物3，4和7 - 10使用3-（4,5-二甲基噻唑-2-基）-2-溴5-二苯基四唑鎓测定法对宫颈癌细胞（HeLa）和正常肾细胞（HEK）进行了评估。其中，金刚烷基取代的锡配合物9和10表现出更高的活性，IC 50值为0.51±0.01和0.41±0.03（μM），并且具有良好的选择性。基于荧光染料（Hoechst 33342 /碘化丙啶和a啶橙/溴化乙锭）的双重染色，细胞死亡机制被鉴定为凋亡，并且可能与活性氧有关。
更新日期：2020-11-10
中文翻译：
具有半刚性异位羟基羰基羧酸配体的Triorganotin（IV）衍生物：合成，表征和细胞毒性
使用由半刚性芳族重氮骨架分隔并带有不同空间位阻的烷基（H'HL 1，环丙基；H'HL 2，环己基；H'HL 3，金刚烷基）隔开的三种有机羟基羧酸。它们与合适的三有机锡前体的反应产生10种组成的复合物：[Me 3 Sn（HL 1）] n ·0.5nC 6 H 5 CH 3 1，[Et 3 Sn（HL 1）] n 2，[ n Bu 3 Sn （HL 1）]n 3，[Ph 3 Sn（HL 1）] n 4，[Me 3 Sn（HL 2）] 2 ·2CH 2 Cl 2 5，[Et 3 Sn（HL 2）] 2 6，{[ n Bu 3 Sn （HL 2）] [ n Bu 3 Sn（HL 2）（H 2 O）]} 7，[Ph 3 Sn（HL 2）] n ·nC 2 H 5 OH 8，[n Bu 3 Sn（HL 3）] n 9和[Ph 3 Sn（HL 3）] n 10。1 – 10的固态结构是从单晶X射线衍射研究以及两个前配体：H'HL 1和H'HL 2推导出来的。在固态下，观察到四种不同的扩展结构类型。在化合物1 - 3与锡原子和配体主链（环丙基）小取代基脂族取代基中，观察到基于羧酸类桥接1D配位聚合物，而化合物4和8 - 10与附着在金属和配体（环己基和金刚烷基）的取代基大都是基于heteroditopic的配体的结合1D配位聚合物。尽管具有基本相同的配体构象，但在锡原子上具有较小取代基的化合物（5，R = Me；6，R = Et）包含24元大环结构。在7中，水分子与锡原子的一半配位，产生双核碎片{[HL 2 ] [ n Bu 3 Sn] [HL 2 ] [ n Bu 3 Sn（H 2 O）]}，它们通过O连接瓦特 ħ···ö SAL氢键成1D氢键磁带。在溶液中，在锡原子1 - 10被协调到单个单阴离子[HL 1-3 ] -配体分子利用与羧酸酯基anisobidentate协调，如从显示119分的Sn核磁共振光谱的结果。三元的抗增殖活性Ñ丁基，三苯基锡化合物3，4和7 - 10使用3-（4,5-二甲基噻唑-2-基）-2-溴5-二苯基四唑鎓测定法对宫颈癌细胞（HeLa）和正常肾细胞（HEK）进行了评估。其中，金刚烷基取代的锡配合物9和10表现出更高的活性，IC 50值为0.51±0.01和0.41±0.03（μM），并且具有良好的选择性。基于荧光染料（Hoechst 33342 /碘化丙啶和a啶橙/溴化乙锭）的双重染色，细胞死亡机制被鉴定为凋亡，并且可能与活性氧有关。
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