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Novel water soluble half-sandwich complexes of the general formulae [M(η6-p-cym)(ha)]2(CF3SO3)2, [M(η6-p-cym)(ha)Cl] or [M(η6-p-cym)(ha)(py)]X (M = Os, Ru; ha = hydroxamate; py = pyridine; X = Cl− or CF3SO3−), incorporating metal-containing entities and hydroxamates both with potential anti-proliferative features, were prepared and characterized by elemental analysis, spectroscopy (NMR, IR) and ESI mass spectrometry. The X-ray crystal structure of [Ru(η6-p-cym)(μ-meaha)]2(CF3SO3)2 (5), [Os(η6-p-cym)(meaha)Cl] (6), [Ru(η6-p-cym)(phebha)Cl], (9), [Ru(η6-p-cym)(bha)(py)](CF3SO3) (12) and [Ru(η6-p-cym)(phebha)(py)](CF3SO3) (14), 6 is the first published structure of an organometallic Os(II)-hydroxamate reported. The effect of size differences of the metal ions, the steric demand of the RC and RN substituents at the hydroxamate group and the type of the monodentate ligand co-present in the stoichiometry, along with the binding architecture of the half-sandwich metal(II) hydroxamate complexes are discussed. A novel dinuclear, dihydroxo bridged complex [Os(η6-p-cym)(py)(μ-OH)]2(CF3SO3)2 (16) is prepared and characterized by X-ray crystallography. Unexpected formation of a dinuclear oxo bridged OsII/OsVI complex [{Os(η6-p-cym)(meaha)}(μ-O){Os(O)(meaha)2}]Cl (17) occurs, and the crystal and molecular structure has been determined by X-ray method. Complexes 1, 5–8, 10 and 14 were tested for their in vitro cytotoxicity, using human-derived ovarian cancer cell lines (A2780 and A2780 cisR), and showed no anti-proliferative effect in the concentration range (0–200 μM) studied.

Synthesis and X-ray diffraction structures of novel half-sandwich Os(ii)-and Ru(ii)-hydroxamate complexes