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Reversible CO binding by Rh/sub 2/(O/sub 2/CCH/sub 3/)/sub n/(HNOCCH/sub 3/)/sub 4-n/. A spectroscopic and electrochemical investigation

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00238a026· OSTI ID:5036049
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The binding constants for carbon monoxide addition to a series of dirhodium complexes of the form Rh/sub 2/(O/sub 2/CCH/sub 3/)/sub n/(HNOCCH/sub 3/)/sub 4-n/, where n = 0, 2, 3, and 4, were determined in 1,2-dichloroethane and in acetonitrile. At room temperature, either 1:1 or 1:2 CO adducts are observed depending upon the particular combination of bridging ligands and the nature of the solvent. In addition, the stability constants of the CO adducts were found to increase with increasing number of acetamidate bridging ions in the dirhodium complex. Cyclic voltammetry was carried out for the oxidation of Rh/sub 2/(ac)/sub n/(acam)/sub 4-n/ in acetonitrile and dichloroethane under various CO partial pressures. The value of E/sub 1/2/ for the formation of RH/sup II/Rh/sup III/ shifted positively with increasing CO pressure. This positive shift can be associated with log K for the 1:1 CO adduct formation. A linear relationship between log K and E/sub 1/2/ for the first oxidation of Rh/sub 2/(O/sub 2/CCH/sub 3/)/sub n/(HNOCCH/sub 3/)/sub 4-n/ under nitrogen was observed for complexes having n = 0, 1, and 2. Finally, solution infrared spectroscopy of Rh/sub 2/(O/sub 2/CCH/sub 3/)/sub n/(HNOCCH/sub 3/)/sub 4-n/CO species showed that the CO stretching frequencies are lowered as the number of HNOCCH/sub 3/ bridging ligands is increased. The lowest CO stretching frequency in this series occurs for Rh/sub 2/(HNOCCH/sub 3/)/sub 4/CO, which has upsilon/sub CO/ = 2028 cm/sup -1/.
Research Organization:
Univ. of Houston, University Park, TX
OSTI ID:
5036049
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:18; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400400 -- Electrochemistry
ACETONITRILE
ADDUCTS
BINDING ENERGY
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
COMPLEXES
DATA
ENERGY
EXPERIMENTAL DATA
HALOGENATED ALIPHATIC HYDROCARBONS
INFORMATION
INFRARED SPECTRA
LIGANDS
MEDIUM TEMPERATURE
NITRILES
NUMERICAL DATA
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
OXIDES
OXYGEN COMPOUNDS
PARTIAL PRESSURE
PRESSURE DEPENDENCE
RHODIUM COMPLEXES
SOLVENT PROPERTIES
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY