Reaction of cyclopentadienyl ruthenium complexes with a carborane anion: Effect of the spectator ligands on the substitution site

Article abstract of DOI:10.1021/om700305e

The reaction of cyclopentadienyl ruthenium complexes of the type [RuCl(Cp)L₁L₂] (L₁, L₂ = PPh ₃, PMe₂Ph, PMePh₂; L₁L₂ = dppe; L₁L₂ = COD; L₁ = CO, L₂ = PPh₃) with Licarb (Hcarb = 2-Me-1,2-dicarba-closo-dodecaborane) gives two types of complexes, [Ru(H)(C₅H₄-carb)L ₁L₂] or [Ru(carb)(Cp)-L₁L₂], depending on the nature of the coordination set. The structures of [Ru(carb)(Cp)(PMe₂Ph)₂] and [RuCl(η⁵-C ₅Me₄H)(PMe₂Ph)₂] have been determined by single-crystal crystallography. The role played by the ligand set on the site of nucleophilic attack is discussed in light of the steric crowding and electronic density at the metal center.