A series of new Ru(ll) arene phosphine complexes derived from Binap have been prepared. Specifically, reaction of Ru(OAc)(2)(Binap) with 3,5-(CF3)(2)C6H3)(4)B (BArF).H(OEt2)(2), is shown to afford new mono- and dinuclear Ru(ll) hydroxyphosphine pi-arene complexes via a series of P-C bond cleavage reactions. The dinuclear Ru(ll) pi-arene complexes contain bridging P(O)(OH)(2) ligands. Crystal structures of five new complexes are reported and suggest an eta(4) -arene rather than an eta(6) -arene coordination mode. However, in solution, their C-13 NMR data are more consistent with a strongly distorted eta(6)-coordination mode. PGSE H-1 and F-19 diffusion measurements on the dinuclear complexes suggest hydrogen bonding of the triflate anion and ion-pairing of the BArF- anion.