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Infrared, Raman, resonance Raman, and excitation profile studies of Rh/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/(PPh/sub 3/)/sub 2/ and its /sup 18/O and CD/sub 3/ isotopomers

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00286a005· OSTI ID:5776064
;
The resonance Raman spectra of RH/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/(PPh/sub 3/)/sub 2/ and its /sup 18/O and CD/sub 3/ isotopomers have been recorded at ca. 80 K. A band at 289 cm/sup /minus/1/, denoted /nu//sub 1/, is assigned to /nu/(Rh-Rh) and is the dominant progression-forming mode. This band also forms combinations with bands attributable to the tetraacetate cage, such as /nu/(Rh-O) and /delta/(OCO), as well as with those of the axial PPh/sub 3/ ligands. Excitation profiles of /nu/(Rh-Rh) and several other bands are shown to maximize under the 376-nm electronic absorption band, which, by way of Raman band depolarization ratio measurements, is assigned to an axial (z) polarized transition terminating in /sigma/* (RhRh). Band assigned to /nu/(Rh-O) are shown to be dependent on both /sup 18/O and CD/sub 3/ substitution. For Rh/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/(PPh/sub 3/)/sub 2/. Raman spectra obtained with 514.5-nm excitation are also discussed. FTIR spectra (3500-40 cm/sup /minus/1/) of Rh/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/(PPh/sub 3/)/sub 2/ and its /sup 18/O and CD/sub 3/ isotopomers are also presented and assigned. The results provide a firm basis for making vibrational band assignments for other dimetal tetracarboxylates. 18 references, 4 figures, 5 tables.
Research Organization:
Univ. College London (England)
OSTI ID:
5776064
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:13; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
AROMATICS
COMPLEXES
DATA
DEUTERIUM
EVEN-EVEN NUCLEI
EXPERIMENTAL DATA
HYDROGEN ISOTOPES
INFORMATION
INFRARED SPECTRA
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
OXYGEN 18
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
RAMAN SPECTRA
RHODIUM COMPLEXES
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES