Electronic structure of metal clusters. 5. Photoelectron spectra and molecular orbital calculations of hydrogen- and halogen-bridged triosmium decacarbonyls
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The gas-phase, ultraviolet photoelectron (PE) spectra and molecular orbital (MO) calculations are reported for (μ-H)-(μ-X)Os3(CO)10 and (μ-X)2Os3(CO)10 (X = CI, Br, I). We observe a loss of intensity in the ionization region of the Os-Os bonds compared to that of Os3(CO)12. The MO calculations suggest that the only direct Os-Os bonds in both of these bridging series are the two (CO)4Os-Os(CO)3 bonds. The (CO)3Os-Os(CO)3 interaction in the (μ-H)(μ-X) series is weakly bonding, while that in the (μ-X)2 series is weakly antibonding. Shifts in the positions of the ionizations due to the t2g-like orbitals are observed. The MO calculations suggest that the t2g-like Os(CO)3 orbitals, which are usually considered only M-CO π bonding, interact strongly with the bridging H and halogen atoms to produce the observed shifts. © 1983, American Chemical Society. All rights reserved.
author list (cited authors)
Chesky, P. T., & Hall, M. B.