Metal-ligand cooperative activation of element-hydrogen bonds (element = C, N, O, Cl, B) on a dinuclear ruthenium bridging imido complex

Abstract

The diruthenium imido complex [(Cp*Ru)2(μ-NPh)(μ-CH2)] (1; Cp* = η5-C5Me5) reacts with a variety of Brønsted acidic element-hydrogen bonds to give amido complexes of the type [(Cp*Ru)2(μ-NHPh)(X)(μ-CH2)]. Single-crystal X-ray structures are reported for products with X = OTf, μ-Cl, μ-κ2-O,O′-O2CPh, μ-NHSO2Ph, μ-H (from i-PrOH), and μ-CCC6H4Me-p, where the Ru–Ru distance ranges from 2.46 Å to 2.68 Å depending on the nature of the ligand X. Additionally, the reaction of 1 with BH3·THF produces the imido-borane adduct [(Cp*Ru)2(μ-H3BNPh)(μ-CH2)], in which two B–H bonds are weakened through the formation of B–H–Ru bridging hydride structures.