The solvento complex [RuH(η¹-OCMe₂)(CO)₂(PPrⁱ₃)₂]BF₄2, which is an active catalyst for the exclusive hydrogenation of phenylacetylene to styrene and the hydrosilylation of the same alkyne to cis-PhCHCH(SiEt₃), was prepared by reaction of [Ru(H)Cl(OC)₂(Prⁱ₃P)₂]1 with AgBF₄ in acetone as solvent. The reactivity of 2 has been investigated. This compound reacts with Lewis bases (L) to give [RuH(CO)₂L(PPrⁱ₃)₂]BF₄[L = H₂O 3, MeCN 4, CO 5 or pyrazole (Hpz)6]. Complex 5 can be deprotonated by KOH to afford [Ru(OC)₃(Prⁱ₃P)₂]7, while the reaction of 6 with [{Rh(µ-OMe)(diolefin)}₂][diolefin = tetrafluorobenzobarrelene (tfbb) or cycloocta-1,5-diene, (cod)] led to heterobinuclear compounds of formula [(OC)₂(Prⁱ₃P)₂Ru(µ-H)(µ-pz)Rh(diolefin)]BF₄(diolefin = tfbb 10 or cod 11). The molecular structure of 11 was determined by an X-ray investigation. Compound 11 crystallises in the orthorhombic space group Fdd2, with cell dimensions a= 28.290(2), b= 22.572(1), c= 23.126(1)Å and Z= 16. The structure was refined to R and R′ values of 0.0232 and 0.0258 for 6297 observed reflections. The cation in 11 can be described as a ruthenium–rhodium heterobinuclear species where the metals are connected through a bidentate pyrazolate group and a bridging hydrodo ligand. The metal–metal distance is 3.1323(3)Å. Complex 2 reacts with HCl to give [RuCl₂(CO)₂(PPrⁱ₃)₂]12, which can be also prepared by reaction of [RuCl(η¹-OCMe₂)(CO)₂-(PPrⁱ₃)₂]BF₄13 with NaCl. This compound in the presence of Lewis bases affords [RuCl(CO)₂L-(PPrⁱ₃)₂]BF₄(L = H₂O 14, MeCN 15, CO 16 or Hpz 17). The reactions of 17 with [{Rh(µ-OMe)(diolefin)}₂] lead to [(OC)₂(Prⁱ₃P)₂Ru(µ-Cl)(µ-pz)Rh(diolefin)]BF₄(diolefin = tf bb 18 or cod 19). Carbon disulfide, SCNR (R = Me or Ph) and HCCCO₂Me, undergo insertion reactions into the Ru–H bond of 2 to give the corresponding insertion products. [Ru(η²-S₂CH)(CO)₂(PPrⁱ₃)₂]BF₄20, [Ru{η²-SN(R)CH}(CO)₂(PPrⁱ₃)₂]BF₄(R = Me 21 or Ph 22) and [[graphic omitted]OMe]CH₂}(CO)₂(PPrⁱ₃)₂]BF₄23.