Department of Chemical and Pharmaceutical Sciences, Via L. Giorgieri 1, 34127 Trieste, Italy.
Dalton Trans. 2012 Jun 28;41(24):7358-71. doi: 10.1039/c2dt30654a. Epub 2012 May 11.
With the aim of expanding the structure-activity relationship investigation, the series of Ru(II) half sandwich coordination compounds of the type Ru([9]aneS3)(chel)(L) previously described by us (where [9]aneS3 is the neutral face-capping ligand 1,4,7-trithiacyclononane, chel is a neutral or anonic chelating ligand, L = Cl(-) or dmso-S, n = 0-2) was extended to 1,4,7-triazacyclononane ([9]aneN3). In addition, new neutral N-N, and anionic N-O and O-O chelating ligands, i.e. dach (trans-1,2-diaminocyclohexane), pic(-) (picolinate), and acac(-) (acetylacetonate), were investigated in combination with both [9]aneS3 and [9]aneN3. Overall, ten new half-sandwich complexes were prepared and fully characterized and their chemical behaviour in aqueous solution was established. The single-crystal X-ray structures of eight of them, including the versatile precursor [Ru([9]aneN3)(dmso-S)(2)Cl]Cl (9), were also determined. The results of in vitro antiproliferative tests performed on selected compounds against MDA-MB-231 human mammary carcinoma cells confirmed that, in this series, only compounds that hydrolyse the monodentate ligand at a reasonable rate show moderate activity, provided that the chelate ligand is a hydrogen bond donor.
为了扩展结构-活性关系的研究，我们之前描述过一系列 Ru(II) 半三明治配位化合物，属于[Ru([9]aneS3)(chel)(L)]+(n+)类型（其中[9]aneS3 是中性面封配体 1,4,7-三硫杂环壬烷，chel 是中性或阴离子螯合配体，L = Cl(-) 或 dmso-S，n = 0-2），现在将其扩展到 1,4,7-三氮杂环壬烷([9]aneN3)。此外，还研究了新的中性 N-N、阴离子 N-O 和 O-O 螯合配体，即 dach（反式-1,2-二氨基环己烷）、pic(-)（吡啶甲酸根）和 acac(-)（乙酰丙酮根），与[9]aneS3 和[9]aneN3 一起使用。总共制备了十种新的半三明治配合物，并对其进行了全面表征，确定了它们在水溶液中的化学行为。其中八种的单晶 X 射线结构，包括多功能前体[Ru([9]aneN3)(dmso-S)(2)Cl]Cl(9)，也被确定。对选定化合物在 MDA-MB-231 人乳腺癌细胞上进行的体外抗增殖测试的结果表明，在该系列中，只有那些以合理速率水解单齿配体的化合物才显示出适度的活性，前提是螯合配体是氢键供体。
