SYNTHESIS AND REACTIVITY OF MONONUCLEAR ANIONIC PENTAFLUOROPHENYL COMPOUNDS OF RHODIUM(I) AND IRIDIUM(I) - X-RAY STRUCTURE OF [(P(OPH)(3))(2)(C6F5)(2)RHAG(PPH(3))]

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)C l(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 tetrab utylammonium salts. The reactivity of some of these complexes have bee n explored. Addition of neutral ligands to [Rh(C6F5)Cl(CO)(2)](-) give s 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)); wit h bis(diphenylphosphino)methane (dppm), the A-frame compound [Rh-2(C6F 5)(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 des cribed. The new compounds I;ave been characterized by elemental analys es, 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 gr oup P (1) over bar) having a unit cell of dimensions a = 11.984(2) Ang strom, 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 me thods 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 C 6F5 (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.