P-C bond splitting reactions in ruthenium(II) complexes of Binap and MeO-Biphep using CF3SO3H and HBF4. A novel Ru-F-H interaction

Reaction of Ru(OAc)(2)(1 or 2), 1 = racemic Binap, or 2 = racemic MeO-Biphe p, with wet CF3SO3H in 1,2-dichloroethane at 363 K results in P-C bond brea king to afford the cationic triflates [Ru(CF3SO3)(6'-diphenylphosphino-1-na phthyl)(PPh2OH)](CF3SO3), 7a, and [Ru(CF3SO3)(6'-diphenylphosphino-1'-(2-di methoxy)biphenyl)PPh2OH)](CF3SO3), 7b. Formally, the H+ protonates the acet ate and water adds across the P-C bond with the resulting arene ring comple xed eta(6) to the Ru(II). The solid-state structures of 7a and 7b are repor ted. A related reaction of Ru(OAc)(2)(1 or 2) with HBF4 gives P-C bond clea vage with the formation of compounds that contain the new phosphinite anion , 6 (C12H11BF2O2P), derived from hydrolysis of the BF4- anion. NMR studies at 213 K on the reaction mixture derived from Ru(OAc)(2)(1) and HBF4 show a n HF addition product containing a Ru-F---H moiety with (1)J(F-19,H-1) = 66 Hz. Warming of this mixture to 273 K gives P-C bond breaking and isolable complexes, 9, containing the fluorophosphine, Ph2PF. Complex 10, a Ru-Cl an alogue of 9 with complexed Ph2PF, has also been isolated.