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Metal core binding energy and charge delocalization in (Os(NH/sub 3/)/sub 4/ClN/sub 2/Cl(NH/sub 3/)/sub 4/Os)Cl/sub 3/, a binuclear mixed-valence osmium complex: an ESCA study

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00519a030· OSTI ID:5740598
 [1];
  1. City Univ. of New York, Bronx
+ Show Author Affiliations

The measurement of the Os 4f spectrum of ((Os(NH/sub 3/)/sub 4/Cl)/sub 2/N/sub 2/)Cl/sub 3/ was repeated. Only one set of Os 4f spin-orbit coupled peaks was seen, with some relatively weak satellites (approx. 13% of the main peak) on the high binding energy side of the spectrum. This, the first observation of only one set of lines in a well-characterized ligand bridged binuclear transition metal mixed-valence compared is clear confirmation of the fact that here one has a single delocalized initial state. For points of comparison, Os 4f spectra were obtained from (Os(NH/sub 3/)Cl)Cl/sub 2/, an Os(III) compound, and (Os(NH/sub 3/)/sub 5/N/sub 2/)Cl/sub 2/, and Os(II) compound. The presence of satellites in the Os(II) compounds, (Os(NH/sub 3/)/sub 5/N/sub 2/)Cl/sub 2/ and the mixed-valence compounds, may be associated with the N/sub 2/ ligand. N/sub 2/ is isoelectronic with CO; and in addition, the ..pi.. back-bonding effect is very strong in Os(II) analogous to some metal carbonyls. The ground- and excited-state levels arising from N/sub 2/ and Os(II) interaction may induce, during photoemission, monopole transitions which give rise to observable satellites. 1 figure, 1 table. (DP)

OSTI ID:
5740598
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:25; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
BINDING ENERGY
CARBONYL RADICALS
COMPLEXES
CRYOGENIC FLUIDS
ELEMENTS
ENERGY
FLUIDS
LIGANDS
NITROGEN
NONMETALS
OSMIUM COMPLEXES
RADICALS
SPECTRA
TRANSITION ELEMENT COMPLEXES
X-RAY SPECTRA