TY - JOUR
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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U2 - 10.1021/ic00193a050
DO - 10.1021/ic00193a050
M3 - Article
AN - SCOPUS:0000853147
SN - 0020-1669
VL - 23
SP - 4361
EP - 4365
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 25
ER -