Photodetachment of free hexahalogenometallate doubly charged anions in the gas phase:: [ML6]2-, (M=Re, Os, Ir, Pt; L=Cl and Br)

We report the first observation and photodetachment photoelectron spectroscopic study of a series of hexahalogenometallates dianions MCl62- (M=Re, Os, Ir, and Pt) and MBr62- (M=Re, Ir, and Pt) in the gas phase. All of these species were found to be stable as free gaseous doubly charged anions. Photoelectron spectra of all the dianions were obtained at several detachment photon energies. The photon-energy-dependent spectra clearly revealed the dianion nature of these species and allowed the repulsive Coulomb barriers to be estimated. The binding energies of the second excess electron in MCl62- (M=Re, Os, Ir, Pt) were determined to be 0.46 (5), 0.46 (5), 0.82 (5), and 1.58 (5) eV, respectively, and those in MBr62- (M=Re, Ir, Pt) to be 0.76 (6), 0.96 (6), and 1.52 (6) eV, respectively. A wealth of electronic structure information about these metal complexes were obtained and low-lying and highly-excited electronic states of the corresponding singly charged anions were observed. Detachment from metal d orbitals or ligand orbitals were observed and could be clearly distinguished; detachments from the metal d-orbitals all occur at low binding energies whereas those from the ligand-dominated orbitals all take place at rather high binding energies. We also found a remarkable correlation between electron affinities measured in vacuo and the redox potentials obtained in the solution phase of these species. (C) 1999 American Institute of Physics. [S0021-9606(99)00234-2].