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)L3 (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.