Synthesis, reactivity, spectroscopic characterization, X-ray structures, PGSE, and NOE NMR studies of (eta5-C5Me5)-rhodium and -iridium derivatives containing bis(pyrazolyl)alkane ligands

Rhodium(III) and iridium(III) complexes containing bis(pyrazolyl)methane ligands (pz = pyrazole, L' in general; specifically, L1 = H2C(pz)2, L2 = H2C(pzMe2)2, L3 = H2C(pz4Me)2, L4 = 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 L1 and L2 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 (rH) and, consequently, the hydrodynamic volume (VH) of all the species have been determined from the measured translational self-diffusion coefficients (Dt), 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].