Abstract
Ruthenium complexes bearing a xanthene-based bis(silyl) chelate ligand without CO ligands, Ru(κ3Si,O,Si-xantsil)(H)[PCy2(η3-C6H8)] (1) and Ru(κ2Si,Si-xantsil)(η6-toluene)(L) (L = cyclooctene (coe) (2) and PPh3 (3)), were synthesized by reactions of Ru(η3-2-methylallyl)2(cod) (A, cod = 1,5-cyclooctadiene) with 4,5-bis(dimethylsilyl)-9,9-dimethylxanthene (xantsilH2) in the presence of phosphines PR3 (R = cyclohexyl (Cy), cyclopentyl (Cyp), and Ph) in cyclohexane or toluene at 60 °C. Complexes 1–3 were fully characterized by X-ray crystallography and NMR spectroscopy. In the case of the reaction with PCy3, complex 1 bearing a phosphine–η3-cyclohexenyl chelate ligand was formed via activation of three sp3-C–H bonds on a cyclohexyl group and hydrogenation of 1,5-cyclooctadiene to cyclooctene. Complex 3 was found to undergo exchange of the η6-toluene ligand with benzene at room temperature.
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