Diiron(ii) pentacarbonyl complexes as CO-releasing molecules: their synthesis, characterization, CO-releasing behaviour and biocompatibility
Diiron(ii) pentacarbonyl complexes as CO-releasing molecules: their synthesis, characterization, CO-releasing behaviour and biocompatibility
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二铁(ii)五羰基配合物作为CO释放分子：其合成、表征、CO释放行为和生物相容性
DOI：
10.1039/c8dt03982h
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发表时间：
2019
影响因子：
4
通讯作者：
He Yi
中科院分区：
文献类型：
--
作者：
Xiao Zhiyin;Jiang Ran;Jin Jing;Yang Xiuqin;Xu Binyu;Liu Xiaoming;He Yabing;He Yi
[Fe(CO)4X2]与单硫酸盐反应，合成了四个二铁（II）羰基配合物[Fe2(μ-SR)3(CO)5X] （X−= Br−,I−;R = CH2CH3, CH2CH2CH3）。它们作为一氧化碳释放分子（corm）的潜力被系统地研究了，揭示了它们的一氧化碳释放行为是高度依赖溶剂的。在二甲亚砜（DMSO）中，co的释放速度较快。氧化态较低的中间产物可能参与反应。相反，在极性较低的溶剂如甲醇、乙腈和二氯甲烷中，分离到具有三铁羰基阳离子的中间体[Fe3(μ-SCH2CH3)6(CO)6]+。三铁中间体进一步分解释放CO。其中一种碘配合物在PBS溶液中与DMSO在脱氧- mb存在下溶解时，也检测了其CO释放，发现CO释放是定量的。此外，进行了动力学分析，co的释放总体上符合一级动力学模型。对母体配合物和三铁中间体提出了似是而非的共释放途径。细胞毒性评估表明，二铁（II）配合物的细胞毒性随卤化物和硫酸盐的不同而变化，而那些含有溴的配合物和具有较长链的硫酸盐更具有生物相容性。
Four diiron(II) carbonyl complexes, [Fe2(μ-SR)3(CO)5X] (X− = Br−, I−; R = CH2CH3, CH2CH2CH3) were facilely synthesized by reacting [Fe(CO)4X2] with monothiolates. Their potential as carbon monoxide-releasing molecules (CORMs) was systematically investigated, revealing that their CO-releasing behaviour is highly solvent-dependent. Specifically, in dimethyl sulfoxide (DMSO), the CO-releasing kinetics were fast. Intermediates with a lower oxidation state might be involved in the reaction. By contrast, in less polar solvents such as methanol, acetonitrile and dichloromethane, intermediates featuring the triiron carbonyl cation, [Fe3(μ-SCH2CH3)6(CO)6]+, were isolated. The triiron intermediate underwent further decomposition to liberate CO. One of the iodo complexes was also examined for its CO-release in PBS solution when solubilised with DMSO in the presence of deoxy-Mb and the CO-release was found to be quantitative. Furthermore, kinetic analyses were performed and the CO-release in general obeyed a first-order kinetic model. Plausible CO-releasing pathways are proposed for the parent complexes and the triiron intermediate. Assessments in cytotoxicity indicated that the cytoxicity of the diiron(II) complexes varied with both the halide and thiolate and those bearing bromide and the thiolate with longer chains were more biocompatible.