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

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

doi:10.1021/ic00193a050

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

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

Chemistry and Biochemistry

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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, fac-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 d_π 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 language	English (US)
Pages (from-to)	4361-4365
Number of pages	5
Journal	Inorganic Chemistry
Volume	23
Issue number	25
DOIs	https://doi.org/10.1021/ic00193a050
State	Published - Jun 1984

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{1ef123388ac54f55aaf060cdfc4c0a3f,

title = "Ligand additivity in the valence photoelectron spectroscopy of phosphine-substituted molybdenum carbonyls",

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, fac-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.",

author = "Bursten, {Bruce E.} and Darensbourg, {Donald J.} and Kellogg, {Glen E.} and Lichtenberger, {Dennis L.}",

year = "1984",

month = jun,

doi = "10.1021/ic00193a050",

language = "English (US)",

volume = "23",

pages = "4361--4365",

journal = "Inorganic Chemistry",

issn = "0020-1669",

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T1 - Ligand additivity in the valence photoelectron spectroscopy of phosphine-substituted molybdenum carbonyls

AU - Bursten, Bruce E.

AU - Darensbourg, Donald J.

AU - Kellogg, Glen E.

AU - Lichtenberger, Dennis L.

PY - 1984/6

Y1 - 1984/6

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

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