Comparison of thionitrosyl and nitrosyl bonding in dicarbonyl(eta/sup 5/-cyclopentadienyl)chromium complexes by gas-phase ultraviolet and x-ray photoelectron spectroscopy

Journal Article · Wed Nov 06 04:00:00 EST 1985 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00217a028· OSTI ID:6036433

Lichtenberger, D L; Hubbard, J L

The gas-phase He I/He II UPS and Mg K..cap alpha.. XPS data for the compounds (eta/sup 5/-C/sub 5/H/sub 5/)Cr(CO)/sub 2/NO and (eta/sup 5/-C/sub 5/H/sub 5/)Cr(CO)/sub 2/NS are reported. The first ionization potentials for the two complexes are nearly the same. A short C-O stretching progression in the first ionization band of the nitrosyl compound shows that it is predominantly associated with metal d character and is symmetrically ..pi.. delocalized into the carbonyls. The next two ionizations for both complexes are sensitive to the ..pi.. symmetry interaction with the NO or NS group. These ionizations are slightly destabilized and are sharper for the NS complex relative to the NO complex, showing stronger metal ..pi.. interaction with both the NS ..pi.. bond and ..pi..* orbitals. The nitrogen 1s binding energy for the NS complex is almost 2 eV lower than that for the NO complex, suggesting a much more negative charge on the NS nitrogen. In contrast, the chromium, carbon, and oxygen core binding energies do not differ significantly between the two complexes. A formal potential model analysis of the (Cr-N-O) and (Cr-N-S) XPS shifts indicates a slightly more positive metal in the NS complex. These results are in agreement with Fenske-Hall approximate calculations and with other physical properties of the two compounds. 25 references, 10 figures, 4 tables.

• Research Organization: Univ. of Arizona, Tucson
• DOE Contract Number: AC02-80ER10746
• OSTI ID: 6036433
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:23; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
BINDING ENERGY
CARBONYLS
CHROMIUM COMPLEXES
COMPARATIVE EVALUATIONS
COMPLEXES
CYCLOALKENES
CYCLOPENTADIENE
DATA
DIENES
ELECTROMAGNETIC RADIATION
ELECTRON SPECTROSCOPY
ELEMENTS
ENERGY
EXPERIMENTAL DATA
FLUIDS
GASES
HELIUM
HYDROCARBONS
INFORMATION
IONIZING RADIATIONS
KINETIC ENERGY
NITROSO COMPOUNDS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
POLYENES
RADIATIONS
RARE GASES
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
ULTRAVIOLET RADIATION
VALENCE
X RADIATION