The electronic nature of the metal-metal quadruple bond: Variable photon energy photoelectron spectroscopy of Mo[sub 2](O[sub 2]CCH[sub 3])[sub 4]

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...

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Veröffentlicht in:Journal of the American Chemical Society 1992-12, Vol.114:26
Hauptverfasser: Lichtenberger, D.L., Ray, C.D., Stepniak, F., Yu Chen, Weaver, J.H.
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Ray, C.D.
Stepniak, F.
Yu Chen
Weaver, J.H.
description 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]] orbital 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.
doi_str_mv 10.1021/ja00052a053
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Also, in the case of the [sigma] component, there is a possible filled/filled interaction between the Mo 4d[sub z[sup 2]] orbital on one metal and the Mo 4p[sub z] orbital on the adjoining metal. 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Also, in the case of the [sigma] component, there is a possible filled/filled interaction between the Mo 4d[sub z[sup 2]] orbital on one metal and the Mo 4p[sub z] orbital on the adjoining metal. 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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]] orbital 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.</abstract><cop>United States</cop><doi>10.1021/ja00052a053</doi></addata></record>
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source American Chemical Society Journals
subjects 400201 - Chemical & Physicochemical Properties
400500 - Photochemistry
ACETATES
CARBOXYLIC ACID SALTS
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
IONIZATION
MOLYBDENUM COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
PHOTOIONIZATION
REFRACTORY METAL COMPOUNDS
RESONANCE
SPECTROSCOPY
THIN FILMS
TRANSITION ELEMENT COMPOUNDS
title The electronic nature of the metal-metal quadruple bond: Variable photon energy photoelectron spectroscopy of Mo[sub 2](O[sub 2]CCH[sub 3])[sub 4]
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