Ligand additivity in the valence photoelectron spectroscopy of phosphine-substituted molybdenum carbonyls

Bruce E. Bursten, Donald J. Darensbourg, Glen E. Kellogg, Dennis L Lichtenberger

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Abstract

The He I valence photoelectron spectra in the 6-9-eV ionization region are reported for the following complexes: Mo-(CO)5PMe3, cis-Mo(CO)4(PMe3)2, trans-Mo(CO)4(PMe3)2, trans-Mo(CO)3(PMe3)3, Mo(CO)5PEt3, trans-Mo(CO)4(PEt3)2, Mo(CO)5P-n-Bu3, and trans-Mo(CO)4(P-n-Bu3)2. The observation of vibrational structure due to excitation of a CO stretching mode in several of the spectra aids band assignment. These data are used to test the validity of the model of ligand additivity for determining the energetics of the dπ electrons in octahedral d6 complexes. It is shown that the model successfully correlates the positions, intensities, and number of the ionization bands for the above compounds. A comparison of the results for the complexes of different phosphine ligands indicates that PMe3, PEt3, and P-n-Bu3 are comparable π-acceptors, but that the σ-donor strength increases as PMe3 < PEt3 < P-n-Bu3.

Original languageEnglish (US)
Pages (from-to)4361-4365
Number of pages5
JournalInorganic Chemistry
Volume23
Issue number25
StatePublished - 1984

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phosphine
Molybdenum
Carbon Monoxide
Photoelectron spectroscopy
phosphines
molybdenum
photoelectron spectroscopy
Ligands
valence
ionization
ligands
photoelectrons
excitation
Ionization
electrons

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Ligand additivity in the valence photoelectron spectroscopy of phosphine-substituted molybdenum carbonyls. / Bursten, Bruce E.; Darensbourg, Donald J.; Kellogg, Glen E.; Lichtenberger, Dennis L.

In: Inorganic Chemistry, Vol. 23, No. 25, 1984, p. 4361-4365.

Research output: Contribution to journalArticle

Bursten, Bruce E. ; Darensbourg, Donald J. ; Kellogg, Glen E. ; Lichtenberger, Dennis L. / Ligand additivity in the valence photoelectron spectroscopy of phosphine-substituted molybdenum carbonyls. In: Inorganic Chemistry. 1984 ; Vol. 23, No. 25. pp. 4361-4365.
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abstract = "The He I valence photoelectron spectra in the 6-9-eV ionization region are reported for the following complexes: Mo-(CO)5PMe3, cis-Mo(CO)4(PMe3)2, trans-Mo(CO)4(PMe3)2, trans-Mo(CO)3(PMe3)3, Mo(CO)5PEt3, trans-Mo(CO)4(PEt3)2, Mo(CO)5P-n-Bu3, and trans-Mo(CO)4(P-n-Bu3)2. The observation of vibrational structure due to excitation of a CO stretching mode in several of the spectra aids band assignment. These data are used to test the validity of the model of ligand additivity for determining the energetics of the dπ electrons in octahedral d6 complexes. It is shown that the model successfully correlates the positions, intensities, and number of the ionization bands for the above compounds. A comparison of the results for the complexes of different phosphine ligands indicates that PMe3, PEt3, and P-n-Bu3 are comparable π-acceptors, but that the σ-donor strength increases as PMe3 < PEt3 < P-n-Bu3.",
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N2 - The He I valence photoelectron spectra in the 6-9-eV ionization region are reported for the following complexes: Mo-(CO)5PMe3, cis-Mo(CO)4(PMe3)2, trans-Mo(CO)4(PMe3)2, trans-Mo(CO)3(PMe3)3, Mo(CO)5PEt3, trans-Mo(CO)4(PEt3)2, Mo(CO)5P-n-Bu3, and trans-Mo(CO)4(P-n-Bu3)2. The observation of vibrational structure due to excitation of a CO stretching mode in several of the spectra aids band assignment. These data are used to test the validity of the model of ligand additivity for determining the energetics of the dπ electrons in octahedral d6 complexes. It is shown that the model successfully correlates the positions, intensities, and number of the ionization bands for the above compounds. A comparison of the results for the complexes of different phosphine ligands indicates that PMe3, PEt3, and P-n-Bu3 are comparable π-acceptors, but that the σ-donor strength increases as PMe3 < PEt3 < P-n-Bu3.

AB - The He I valence photoelectron spectra in the 6-9-eV ionization region are reported for the following complexes: Mo-(CO)5PMe3, cis-Mo(CO)4(PMe3)2, trans-Mo(CO)4(PMe3)2, trans-Mo(CO)3(PMe3)3, Mo(CO)5PEt3, trans-Mo(CO)4(PEt3)2, Mo(CO)5P-n-Bu3, and trans-Mo(CO)4(P-n-Bu3)2. The observation of vibrational structure due to excitation of a CO stretching mode in several of the spectra aids band assignment. These data are used to test the validity of the model of ligand additivity for determining the energetics of the dπ electrons in octahedral d6 complexes. It is shown that the model successfully correlates the positions, intensities, and number of the ionization bands for the above compounds. A comparison of the results for the complexes of different phosphine ligands indicates that PMe3, PEt3, and P-n-Bu3 are comparable π-acceptors, but that the σ-donor strength increases as PMe3 < PEt3 < P-n-Bu3.

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