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Synthesis and characterization of (Ru(II), Co(III)) heterobimetallic complexes formed with a 1,10-phenanthroline based hydroxamic acid conjugate
Journal of Organometallic Chemistry ( IF 2.3 ) Pub Date : 2020-04-02 , DOI: 10.1016/j.jorganchem.2020.121265
Imre Nagy , Etelka Farkas , Jana Kasparkova , Hana Kostrhunova , Viktor Brabec , Péter Buglyó

A novel ambidentate type hydroxamic acid derivative (phenhaH, 1) containing an (O,O) and a 1,10-phenantroline (phen) based (N,N) donoratom set together with its heterobimetallic complexes incorporating an octahedral [Co(4 N)]3+ (4 N = tris(2-aminoethyl)amine (tren) or tris(2-methylpyridyl)amine (tpa)) and a half-sandwich type [(η6-p-cym)Ru]2+ entity have been synthesized and characterized using various analytical techniques. Reaction of [Co(4 N)Cl]Cl2 with 1 proved the exclusive (O,O) coordination of the ligand to the [Co(4 N)]3+ core to yield [Co(tpa)(phenha)](ClO4)2, (2). Subsequent treatment of 1 with [Ru(η6-p-cym)Cl2]2 and [Co(4 N)Cl]Cl2 in a one-pot reaction resulted in the formation of [(η6-p-cym)Ru(Cl)(phenha)Co(tren)]Cl(PF6)2 (3) and [(η6-p-cym)Ru(Cl)(phenha)Co(tpa)](PF6)3 (4) in which the organometallic Ru core is coordinated by the phen part while the Co entity by the hydroxamate part of 1. Cyclic voltammetry revealed that 4 could be reduced at a less negative potential and exhibits a reversible Co(III)/Co(II) redox process compared to 3 due to the π-back bonding interaction between the Co(III) centre and the pyridyl-N donors of tpa in 4. Complexes 24 were tested for their in vitro cytotoxicity using human-derived cancer cell lines (HeLa, MCF-7, HCT116 and MDA-MB-231) and showed moderate anti-proliferative activity in the double digit micromolar concentration range, 4 being the most active. Complex 4 displayed better activity against MDA-MB-231 cells than cisplatin.



中文翻译:

与1,10-菲咯啉基异羟肟酸共轭物形成的(Ru(II),Co(III))异双金属配合物的合成与表征

一种新型的双齿型异羟肟酸衍生物(phenhaH,1),其中包含基于(O,O)和1,10-菲咯啉(phen)的(N,N)供体原子,以及包含八面体[Co(4 N )] 3+(4 N =三(2-氨基乙基)胺(TREN)或三(2-甲基吡啶基)胺(TPA))和半夹心型[(η 6 - p -cym)的Ru] 2+实体已经使用各种分析技术对它们进行了合成和表征。[Co(4 N)Cl] Cl 21的反应证明了配体与[Co(4 N)] 3+核的排他(O,O)配位,产生[Co(tpa)(phenha)] ClO 42,(2)。后续处理的1用的[Ru(η 6 - p -cym)氯2 ] 2和[CO(4 N)CL]氯2在一个单釜反应导致的形成[(η 6 - p -cym)的Ru(Cl)的(phenha)的Co(TREN)]氯(PF 623)和[(η 6 - p -cym)的Ru(Cl)的(phenha)的Co(TPA)](PF 634 ),其中有机金属Ru核由phen部分配位,而Co实体由1的异羟肟酸酯部分配位。循环伏安法显示4由于3的Co(III)中心与tpa的吡啶基-N供体之间的π背键相互作用,与3相比较,可以在较低的负电位下还原并表现出可逆的Co(III)/ Co(II)氧化还原过程。4。配合物2 - 4测试它们测试在体外使用人衍生的癌细胞系(HeLa细胞,MCF-7,HCT116和MDA-MB-231)的细胞毒性和在两位数微摩尔浓度范围内表现出中等的抗增殖活性,4感最活跃。复合物4显示出比顺铂更好的针对MDA-MB-231细胞的活性。

更新日期:2020-04-03
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