Quadruple metal-metal bonds with strong donor ligands. Ultraviolet photoelectron spectroscopy of M{sub 2}(form){sub 4} (M = Cr, Mo, W; form = N,N{prime}-diphenylformamidinate)

Journal Article · Wed Dec 29 04:00:00 EST 1999 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja993065e· OSTI ID:20017324

Lichtenberger, D L; Lynn, M A; Chisholm, M H

The He I photoelectron spectra of M{sub 2}(form){sub 4}(M = Cr, Mo, W; form - N,N{prime}-diphenylformamidinate) and Mo{sub 2}(cyform){sub 4} (cyform = N,N{prime}-dicyclohexylformamidinate) are presented. For comparison, the Ne I, He I, and He II photoelectron spectra of Mo{sub 2}(p-CH{sub 3}-form){sub 4} have also been obtained. The valence ionization features of these molecules are interpreted based on (1) the changes that occur with the metal and ligand substitutions, (2) the changes in photoelectron cross sections with excitation source, and (3) the changes from previously studied dimetal complexes. These photoelectron spectra are useful for revealing the effects that better electron donor ligands have on the valence electronic structure of M{sub 2}(L-L){sub 4} systems. Comparison with the He I spectra of the isoelectronic M{sub 2}(O{sub 2}CCH{sub 3}){sub 4} compounds is particularly revealing. Unlike with the more electron-withdrawing acetate ligand, several formamidinate-based ionizations derived from the nitrogen p{sub {pi}} orbitals occur among the metal-metal {sigma}, {pi}, and {delta} ionization bands. Although these formamidinate-based levels are close in energy to the occupied metal-metal bonds, they have little direct mixing interaction with them. The shift of the metal-metal bond ionizations to lower ionization energies for the formamidinate systems is primarily a consequence of the lower electronegativity of the ligand and the better {pi} donation into empty metal levels. The metal-metal {delta} orbital experiences some additional net bonding interaction with ligand orbitals of the same symmetry. Also, an additional bonding interaction from ligand-to-metal electron donation to the {delta}* orbital is identified. These spectra suggest a greater degree of metal-ligand covalency than in the related M{sub 2}(O{sub 2}CCH{sub 3}){sub 4} systems. Fenske-Hall molecular orbital and density functional (ADF) calculations agree with the assignment and interpretation of these spectra. Calculated ionization energies are reported for M{sub 2}(form){sub 4} based on several different density functionals and with different orientations and substitutions for the phenyl rings. It is found that good estimates of the ionization energies are obtained when the truncated system M{sub 2}(HN-(CH)NH){sub 4}, in which the phenyl groups are replaced by hydrogen atoms, is employed.

• Research Organization: Univ. of Arizona, Tucson, AZ (US)
• Sponsoring Organization: National Science Foundation; US Department of Energy
• DOE Contract Number: FG03-95ER14574
• OSTI ID: 20017324
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 51 Vol. 121; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CHEMICAL BONDS
CHROMIUM COMPLEXES
MOLYBDENUM COMPLEXES
ORGANIC NITROGEN COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
TUNGSTEN COMPLEXES