ELECTRONIC-STRUCTURE OF METAL-CLUSTERS .2. PHOTO-ELECTRON SPECTRUM AND MOLECULAR-ORBITAL CALCULATIONS OF DECACARBONYLDIHYDRIDOTRIOSMIUM
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Molecular orbital (MO) calculations and the gas-phase ultraviolet photoelectron (PE) spectrum are reported for H2Os3(CO)10. In a comparsion with the PE spectrum of Os3(CO)12, the major spectral change is loss of a band due to a direct Os-Os bond and appearance of bands due to Os-H-Os bridge bonds. The spectrum also shows a substantial rearrangement of the bands due to the pseudo-t2g electrons, which are usually considered Os-CO bonding but Os-Os nonbonding. The molecular orbital results, which are described in terms of the pseudooctahedral fragments, Os(CO)4 and Os(CO)3, suggest that the rearrangement of the pseudo-t2g electrons results in a partial Os-Os bond between the hydrogen-bridged osmiums. The calculations also suggest that donation into a low-lying Os-Os antibonding orbital is responsible for the increase in Os-Os bond distance as bridging hydrogens are replaced by bridging methoxide groups. 1982, American Chemical Society. All rights reserved.
