PHOTOELECTRON-SPECTRA OF AND MOLECULAR-ORBITAL CALCULATIONS ON (ETA-5-CYCLOPENTADIENYL)DINITROSYLHALOCHROMIUM AND (ETA-5-CYCLOPENTADIENYL)DINITROSYLHALOTUNGSTEN
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The gas-phase ultraviolet photoelectron spectra are reported for the compounds (5-C5H5)M(NO)2X, where M = Cr, W and X = Cl, Br, I. The observed spin-orbit splitting on the heavy atoms is used to assign and interpret the spectra. The results compare favorably with a Fenske-Hall molecular orbital calculation on the (5-C5H5)Cr(NO)2Cl species. Although the complexes are formally M(0) d6, the calculations suggest that the metal electrons are highly delocalized onto the nitrosyls. This suggestion is supported by the similarity in the ionization energies of the chromium complexes to those of the isoelectronic (5-C5H5)Fe(CO)2X systems. Comparison of the ionization energy of the metal-halogen bonds suggests stronger W-X bonds than Cr-X bonds, which is consistent with the reactivity of the complexes and with the relative metal-chloride bond lengths. 1981, American Chemical Society. All rights reserved.
