High-pressure synthesis of [Ru2(μ-dppm)2 (μ-CO)(CO)4, Ru2(μ-dppm)(μ-dmpm) (μ-CO)(CO)4], and [Ru(dcypm)(CO)3] from Ru3(CO)12 and the diphosphines: R2PCH2PR2; R = CH3(dmpm), C6H5 (dppm) and C6H11 (dcypm).

Article abstract of DOI:10.1016/S0277-5387(96)00450-0

The high-pressure (1300 psi CO, 120°C) reactions of Ru₃(CO)₁₂ with the diphosphines R₂PCH₂PR₂; R = CH₃ (dmpm), C₆H₅ (dppm), and C₆H₁₁ (dcypm), are reported. In the case of dppm, the disphosphine-bridged dinuclear ruthenium complex [Ru₂(μ-dppm)₂(μ-CO)(CO)₄] was obtained. The corresponding reaction with dcypm afforded the mononuclear chelated diphosphine complex [Ru(dcypm)(CO)₃]. The mixed ligand system [Ru₂(μ-dppm)(μ-dmpm)(μ-CO)(CO)₄] was obtained by employing a 1 : 1 mixture of dppm and dmpm. The crystal and molecular structures of [Ru₂(μ-dppm)₂(μ-CO)(CO)₄] and [Ru(dcypm)(CO)₃] were also determined.