The electronic nature of the metal-metal quadruple bond: variable photon energy photoelectron spectroscopy of Mo2(O2CCH3)4
| Autor: | Frank Stepniak, Yu Chen, J. H. Weaver, Dennis L. Lichtenberger, Charles D. Ray |
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| Rok vydání: | 1992 |
| Předmět: | |
| Zdroj: | Journal of the American Chemical Society. 114:10492-10497 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja00052a053 |
| Popis: | Variable-energy photoelectron spectroscopy of thin film Mo[sub 2](O[sub 2]CCH[sub 3])[sub 4] on a GaAs substrate in ultrahigh vacuum is used to examine the valence ionizations of the quadruple metal-metal bond. The changes in photoionization cross sections with photon energy over a range of 40 to 90 eV are examined. The metal-based, [sigma], [pi], and [delta] ionizations of the quadruple bond are strongly enhanced relative to the acetate-based ionizations in the region of photon energies from 40 to 50 eV. This is consistent with a molybdenum 4p to 4d resonance and super-Coster-Kronig Auger enhancement of the metal-based ionizations. The extent of resonance enhancement is related to the amount of Mo 4d character associated with the ionization. The [pi] ionization of the Mo-Mo quadruple bond has the largest contribution from the Mo 4d orbitals. The [delta] and [sigma] ionizations of the metal-metal bond contain smaller amounts of Mo 4d character, and some Mo 4d character is observed in the acetate-based ionizations. This is explained in terms of significant overlap and mixing of the [delta] and [sigma] components with the ligand orbitals. Also, in the case of the [sigma] component, there is a possible filled/filled interaction between the Mo 4d[sub z[sup 2]] orbitalmore » on one metal and the Mo 4p[sub z] orbital on the adjoining metal. These interactions have significant impact on the properties of these complexes. 26 refs., 10 figs.« less |
| Databáze: | OpenAIRE |
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