Arylation with [Ag(C6F5)] or (NBu(4))[Ag(C6F5)(2)] of several rhodium or iridium substrates leads to new anionic complexes of type [M(C6F5)Cl(L(2))](-) (M = Rh, L(2) = (CO)2; M = Ir, L(2) = cod) or [M(C6F5)(2)(L(2))](-) (M = Rh, L(2) = (CP)(2), cod, {P(OPh)(3)}(2); M = Ir, L(2) = cod) which have been isolated as benzyltriphenylphosphonium or tetrabutylammonium salts. The reactivity of some of these complexes have been explored. Addition of neutral ligands to [Rh(C6F5)Cl(CO)(2)](-) gives neutral rhodium(I) complexes [Rh(C6F5)(PPh(3))(CO)(2)] and [Rh(C6F5)(CO)L] (L = 2,2’-bipyridine (bipy) or 1,10-phenanthroline (phen)); with bis(diphenylphosphino)methane (dppm), the A-frame compound [Rh-2(C6F5)(2)(mu-CO)mu-dppm)(2)] is prepared. Reactions of methyl iodide, [Tl(C6F5)(2)Cl], and [Ag(PPh(3))](+) with the rhodium(I) complexes are described. The new compounds I;ave been characterized by elemental analyses, MS, NMR, and conductivity and the heterobimetallic complex [{P(OPh)(3))(2)(C6F5)(2)RhAg(PPh(3))] has also been characterized by a single-crystal X-ray diffraction study. The crystals are triclinic (space group P (1) over bar) having a unit cell of dimensions a = 11.984(2) Angstrom, b = 12.752(2) Angstrom, c = 22.183(5) Angstrom, alpha = 101.07(1)degrees, beta = 104.14(1)degrees, gamma = 103.06(1)degrees, V = 3090.7(10) Angstrom 3, and Z = 2. The structure was solved by Patterson methods and refined by full-matrix least squares to R = 0.064, R(w) = 0.051 for 5802 observed reflections (F greater than or equal to 2 sigma(F)). The rhodium atom is in a square-pyramidal environment, with two C6F5 (cis) and two P(OPh)(3) ligands in the square plane and a Ag(PPh(3)) moiety in the apical position. The complex contains a Rh-Ag bond [2.635(1) Angstrom] unsupported by covalent bridges.