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

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00193a050· OSTI ID:5944813
; ; ;

The He I valence photoelectron spectra in the 6-9-eV ionization region are reported for seven phosphine-substituted molybdenum carbonyls. 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..pi.. electrons in octahedral d/sup 6/ complexes. It is shown that the model successfully correlates the positions, intensities, and number of the ionization bands for the molybdenum compounds. A comparison of the results for the complexes of different phosphine ligands indicates that the trimethyl (PMe/sub 3/), triethyl (PEt/sub 3/), and tri-n-butyl (P-n-Bu/sub 3/) phosphines are comparable ..pi..-acceptors, but that the sigma-donor strength increases as PMe/sub 3/ < PEt/sub 3/ < P-n-Bu/sub 3/.

Research Organization:
Ohio State Univ., Columbus
DOE Contract Number:
AC02-80ER10746
OSTI ID:
5944813
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 23:25; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical &amp; Physicochemical Properties
400301* -- Organic Chemistry-- Chemical &amp; Physicochemical Properties-- (-1987)
CARBONYLS
COMPLEXES
DATA
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
INFORMATION
MATHEMATICAL MODELS
MOLYBDENUM COMPLEXES
NUMERICAL DATA
PHOSPHINES
PHOSPHORUS COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES