Cationic rhodium(I) complexes formed in the reactions of HRh(CO)L3 (L = PPh3, P(OPh)3) complexes with silver(I) salts

The reactions of HRh(CO)L-3 (L=PPh3, P(OPh)(3)) complexes with AgY (Y=BF4-, CF3SO3-, PF6-) lead to [Rh(CO)(PPh3)(2)(H2O)]Y and [Rh (CO)(P(OPh)(3))(3)]Y compounds. The solvolysis of [Rh(CO)(PPh3)(2)(H2O)]PF6 in ethanol produced a crystalline trans-[Rh(CO)(PPh3)(2)(OPOF2)] complex containing distorted square-planar rhodium center. The different arrangement of OPOF2- ligands found in two crystallographically independent molecules is connected with the presence of intra- and intermolecular C-H...O hydrogen bonds involving both oxygen atoms of each OPOF2- anion. The reaction of [Rh(CO)(P(OPh)(3))(3)]Y (Y=BF4-, PF6-) in solution with CO leads to [Rh(CO)(2)(P(OPh)(3))(3)]Y and with P(OPh)(3) to [Rh(P(OPh)(3))(4)]Y complexes. The [Rh(P(OPh)(3))(4)]PF6 complex was also obtained as a final reaction product of HRh(P(OPh)(3))(4) with AgPF6. (C) 2003 Elsevier Science B.V. All rights reserved.