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取代基对新型铼(i)醛中膦配体的影响。合成、计算研究及对其抗增殖活性的初步了解。

Influence of the substituent on the phosphine ligand in novel rhenium(i) aldehydes. Synthesis, computational studies and first insights into the antiproliferative activity.

机构信息

Laboratory of Organometallic Chemistry, Faculty of Chemistry and Biology, Universidad de Santiago de Chile, Avda. Libertador Bernardo O'Higgins 3363, Estación Central, Santiago, Chile.

出版信息

Dalton Trans. 2018 Oct 9;47(39):13861-13869. doi: 10.1039/c8dt03160f.

DOI:10.1039/c8dt03160f
PMID:30225486
Abstract

Cyrhetrenyl aldehyde derivatives [(η5-C5H4CHO)Re(CO)2PR3] with R = methyl (Me, 2a), phenyl (Ph, 2b), and cyclohexyl (Cy, 2c) were synthesized by a photochemical reaction from the starting material [(η5-C5H4CHO)Re(CO)3] (1) and the corresponding phosphines. The complexes were fully characterized by FT-IR, 1H, 13C and 31P NMR spectroscopy, elemental analysis and mass spectrometry. The molecular structures of 2a-c have also been determined. Electronic structure calculations by TD-DFT and electrochemical studies are in sound agreement with the effect of the substitution of one carbonyl group by a phosphine ligand. Additionally, the antiproliferative activity of complexes 1 and 2a-c was studied on the human cancer cell lines HT-29 and PT-45 using an MTT assay. Out of all new compounds, only the triphenylphosphine derivative 2b exhibited pronounced cytotoxic effects on both cell lines, being ca. 1.5 times more potent than cisplatin.

摘要

Cyrhetrenyl 醛衍生物 [(η5-C5H4CHO)Re(CO)2PR3],其中 R = 甲基 (Me,2a)、苯基 (Ph,2b) 和环己基 (Cy,2c),是通过起始原料 [(η5-C5H4CHO)Re(CO)3] (1) 和相应的膦的光化学反应合成的。复合物通过 FT-IR、1H、13C 和 31P NMR 光谱、元素分析和质谱进行了充分表征。2a-c 的分子结构也已确定。通过 TD-DFT 的电子结构计算和电化学研究与一个羰基被膦配体取代的效果非常吻合。此外,使用 MTT 测定法研究了配合物 1 和 2a-c 对人类癌细胞系 HT-29 和 PT-45 的抗增殖活性。在所有新化合物中,只有三苯基膦衍生物 2b 对两种细胞系均表现出明显的细胞毒性作用,其效力约为顺铂的 1.5 倍。

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