Electronic structure of metal clusters. 4. Photoelectron spectra and molecular orbital calculations on cobalt, iron, ruthenium, and osmium sulfide nonacarbonyl clusters Academic Article uri icon


  • Gas-phase, ultraviolet photoelectron (PE) spectra and molecular orbital (MO) calculations are reported for SCo 3 (CO) 9 , SH n-1 Fe n Co 3-n (CO) 9 (n = 1-3), S 2 Fe 3 (CO) 9 , and SH 2 M 3 (CO) 9 , (M = Fe, Ru, Os). The first PE spectra reported for mixed-metal clusters are included in this series. As Co atoms are replaced by the isoelectronic FeH unit, the spectra show the loss of a Co band and the appearance of an Fe band. This phenomenon suggests that the d bands localize upon ionization. In a comparison with the PE spectrum of M 3 (CO) 12 (M = Fe, Ru, Os), the major spectral changes for SH 2 M 3 (CO) 9 (M = Fe, Ru, Os) are the loss of a band corresponding to direct M-M interactions and the appearance of bands due to a mixture of energy-equivalent M-H-M and M-S interactions. The spectra also show a substantial rearrangement of the bands due to the t 2g -like electrons, which are usually considered M-CO π bonding. An antibonding interaction between a S orbital and the t 2g -like orbitals is responsible for a unique band in the spectra which occurs at high ionization energy between the M-M bonding band and the main t 2g -like band. © 1983, American Chemical Society. All rights reserved.

author list (cited authors)

  • Chesky, P. T., & Hall, M. B.

citation count

  • 12

publication date

  • October 1983