University of Vienna, Institute of Inorganic Chemistry, Waehringer Str. 42, A-1090, Vienna, Austria.
Dalton Trans. 2010 Aug 21;39(31):7345-52. doi: 10.1039/c003085f. Epub 2010 Jul 2.
The synthesis and in vitro anticancer activity of Os(II)-arene complexes with carbohydrate-derived phosphite co-ligands are reported. The compounds were characterized by standard methods and the molecular structure of dichlorido(eta(6)-p-cymene)(3,5,6-bicyclophosphite-1,2-O-isopropylidene-alpha-D-glucofuranoside)osmium(II) was determined by X-ray diffraction analysis. Complexes with chlorido leaving groups undergo hydrolysis by consecutive formation of aqua compounds, followed by cleavage of a P-O bond of sugar phosphite ligands, as demonstrated by NMR studies. These observations are similar to those of analogous Ru(II)-arene complexes; however the rate of hydrolysis is very slow for osmium compounds. The complexes with oxalato leaving groups resist hydrolysis; no hydrolytic species were detected by (31)P{(1)H} NMR spectroscopy over several days. Within this series of Os compounds, in vitro anticancer activity is highest for the most lipophilic chlorido complex dichlorido(eta(6)-p-cymene)(3,5,6-bicyclophosphite-1,2-O-cyclohexylidene-alpha-D-glucofuranoside)osmium(II).
报道了具有碳水化合物衍生亚膦酸酯共配体的 Os(II)-芳基配合物的合成及体外抗癌活性。通过标准方法对化合物进行了表征，并通过 X 射线衍射分析确定了二氯(η(6)-对-甲基苯)(3,5,6-双环膦酸酯-1,2-O-异丙叉-α-D-葡萄糖呋喃糖苷)合锇(II)的分子结构。具有氯离去基团的配合物通过连续形成水合化合物进行水解，随后糖亚膦酸酯配体的 P-O 键断裂，这一点通过 NMR 研究得到证实。这些观察结果与类似的 Ru(II)-芳基配合物相似；然而，对于锇化合物，水解的速率非常慢。具有草酰根离去基团的配合物抵抗水解；在数天内，通过(31)P{(1)H}NMR 光谱未检测到水解产物。在这一系列 Os 化合物中，最亲脂性的氯配合物二氯(η(6)-对-甲基苯)(3,5,6-双环膦酸酯-1,2-O-环己叉-α-D-葡萄糖呋喃糖苷)合锇(II)具有最高的体外抗癌活性。
