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−Biphep, with wet CF 3 SO 3 H in 1,2-dichloroethane at 363 K results in P−C bond breaking to afford the cationic triflates [Ru(CF 3 SO 3 )(6‘-diphenylphosphino-1-naphthyl)(PPh 2 OH)](CF 3 SO 3 ), 7a, and [Ru(CF 3 SO 3 )(6‘-diphenylphosphino-1‘-(2-dimethoxy)biphenyl)(PPh 2 OH)](CF 3 SO 3 ), 7b . Formally, the H + protonates the acetate and water adds across the P−C bond with the resulting arene ring complexed η 6 to the Ru(II). The solid-state structures of 7a and 7b are reported. A related reaction of Ru(OAc) 2 ( 1 or 2 ) with HBF 4 gives P−C bond cleavage with the formation of compounds that contain the new phosphinite anion, 6 (C 12 H 11 BF 2 O 2 P), derived from hydrolysis of the BF 4 - anion. NMR studies at 213 K on the reaction mixture derived from Ru(OAc) 2 ( 1 ) and HBF 4 show an HF addition product containing a Ru−F- - -H moiety with 1 J ( 19 F, 1 H) = 66 Hz. Warming of this mixture to 273 K gives P−C bond breaking and isolable complexes, 9, containing the fluorophosphine, Ph 2 PF. Complex 10, a Ru−Cl analogue of 9 with complexed Ph 2 PF, has also been isolated.