Rhodium(III) and iridium(III) complexes containing bis(pyrazolyl)methane ligands (pz = pyrazole, L' in general; specifically, L-1 = H2C(pz)(2), L-2 = H2C(pz(Me2))(2), L-3 = H2C(pz(4Me))(2), L-4 = Me2C(pz)(2)), have been prepared in a study exploring the reactivity of these ligands toward [Cp*MCl(mu-Cl)](2) dimers (M = Rh, Ir; Cp* = pentamethylcyclopentadienyl). When the reaction was carried out in acetone solution, complexes of the type [Cp*M(L')Cl]Cl were obtained. However, when L-1 and L-2 ligands have been employed with excess [Cp*MCl(mu-Cl)](2), the formation of [Cp*M(L')Cl][Cp*MCl3] species has been observed. PGSE NMR measurements have been carried out for these complexes, in which the counterion is a cyclopentadienyl metal complex, in CD2Cl2 as a function of the concentration. The hydrodynamic radius (r(H)) and, consequently, the hydrodynamic volume (V-H) of all the species have been determined from the measured translational self-diffusion coefficients (D-t), indicating the predominance of ion pairs in solution. NOE measurements and X-ray single-crystal studies suggest that the [Cp*MCl3](-) approaches the cation, orienting the three Cl-legs of the "piano-stool" toward the CH2 moieties of the bis(pyrazolyl)methane ligands. The reaction of 1 equiv of [Cp*M(L')Cl]Cl or [Cp*M(L')Cl][Cp*MCl3] with 1 equiv of AgX (X = ClO4 or CF3SO3) in CH2Cl2 allows the generation of [Cp*M(L')Cl]X, whereas the reaction of 1 equiv of [Cp*M(L')Cl] with 2 equiv of AgX yields the dicationic complexes [Cp*M(L')(H2O)][X](2), where single water molecules are directly bonded to the metal atoms. The solid-state structures of a number of complexes were confirmed by X-ray crystallographic studies. The reaction of [Cp*Ir(L')(H2O)][X](2) with ammonium formate in water or acetone solution allows the generation of the hydride species [Cp*Ir(L')H][X].