Rhodium(III) Dihalido Complexes: The Effect of Ligand Substitution and Halido Coordination on Increasing Cancer Cell Potency.
Rhodium(III) Dihalido Complexes: The Effect of Ligand Substitution and Halido Coordination on Increasing Cancer Cell Potency.
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DOI：
10.1021/acs.inorgchem.0c03704
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发表时间：
2021-01
影响因子：
4.6
通讯作者：
R. Lord;Markus Zegke;A. M. Basri;C. Pask;P. McGowan
中科院分区：
文献类型：
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作者：
R. Lord;Markus Zegke;A. M. Basri;C. Pask;P. McGowan
合成了8个新的铑（III）二卤代配合物[RhX_2（L）（LH）]（其中X = Cl或I），其中含有两个双齿N-（3-卤代苯基）吡啶酰胺配体。配体在复合物中具有不同的结合模式，其中一个是中性的并且通过N，N（LH）配位结合，而另一个是阴离子的并且通过N，O（L）配位结合。固态和溶液研究证实，当X = Cl时，存在多种异构体;然而，在与碘化钾（X = I）进行卤化物交换后，络合物仅作为单一稳定的反式异构体存在。NMR研究表明Rh（III）反式二碘络合物在水溶液中保持稳定，96 h内没有报道配体交换。针对一系列癌细胞系的化学敏感性数据显示两种细胞毒性复合物，其中L = N-（3-溴苯基）吡啶酰胺配体。结果已与类似的Ru（III）络合物进行了比较，并且总体上突出了Rh（III）反式二碘代络合物的细胞毒性比类似的Rh（III）二氯代络合物高78倍，而不像Ru（III）络合物对所有细胞系都是等毒性的。此外，Rh（III）反式二碘代络合物对癌细胞更具选择性，其选择性指数（SI）值比顺铂对结肠直肠癌高>25倍。
This work presents the synthesis of eight new rhodium(III) dihalido complexes, [RhX2(L)(LH)] (where X = Cl or I), which incorporate two bidentate N-(3-halidophenyl)picolinamide ligands. The ligands have different binding modes in the complexes, whereby one is neutral and bound via N,N (LH) coordination, while the other is anionic and bound via N,O (L) coordination. The solid state and solution studies confirm multiple isomers are present when X = Cl; however, after a halide exchange with potassium iodide (X = I) the complexes exist exclusively as single stable trans isomers. NMR studies reveal the Rh(III) trans diiodido complexes remain stable in aqueous solution with no ligand exchange reported over 96 h. Chemosensitivity data against a range of cancer cell lines show two cytotoxic complexes, where L = N-(3-bromophenyl)picolinamide ligand. The results have been compared to the analogous Ru(III) complexes and overall highlight the Rh(III) trans diiodido complex to be ∼78× more cytotoxic than the analogous Rh(III) dichlorido complex, unlike the Ru(III) complexes which are equitoxic against all cell lines. Additionally, the Rh(III) trans diiodido complex is more selective toward cancerous cells, with selectivity index (SI) values >25-fold higher than cisplatin against colorectal carcinoma.