ELECTRONIC-STRUCTURE OF METAL-CLUSTERS .6. PHOTOELECTRON-SPECTRA AND MOLECULAR-ORBITAL CALCULATIONS OF BIS(MU-3-SULFIDO)NONACARBONYLTRIOSMIUM AND BIS(MU-3-SELENIDO)NONACARBONYLTRIOSMIUM

Gas-phase, ultraviolet photoelectron (PE) spectra and molecular orbital (MO) calculations are reported for Os3(CO)9(3-X)2 (X= S, Se). The spectra are similar to that reported for Fe3(CO)9(3-S)2 but have increased band definition. The HOMO, a 3c-2e (Os-Os-Os) bond, is dominated by the eg-like orbitals of the Os(CO)3 fragment and contains most of the net metal-metal overlap population. Ionization from this orbital occurs at lower energy than the remaining ionizations. The t2g-like orbitals on the Os(CO)3 fragments make little or no net contribution to Os-X or to Os-Os bonding. The eg-like and, to a lesser extent, the a1-like orbitals on the metal fragments are responsible for nearly all of the Os-Os and Os-X (X = S, Se) bonds in the cluster. 1988, American Chemical Society. All rights reserved.

ELECTRONIC-STRUCTURE OF METAL-CLUSTERS .6. PHOTOELECTRON-SPECTRA AND MOLECULAR-ORBITAL CALCULATIONS OF BIS(MU-3-SULFIDO)NONACARBONYLTRIOSMIUM AND BIS(MU-3-SELENIDO)NONACARBONYLTRIOSMIUM Academic Article