Labile behavior of carbonyl ligands in butadienecarbonyl and ethylenecarbonyl complexes of rhodium(I) under the action of 1,5-cyclooctadiene
The processes resulting in the redistribution of the carbonyl groups between the rhodium(I) complexes in a solution of (Rh(C2H4)COCl)2 (I) in chloroform under the action 1,5-cyclooctadiene (cod) have been studied by the methods of IR, TC NMR, and H NMR spectroscopy. It has been shown that in reaction mixtures containing I + x mole cod/Rh the asymmetric complex (cod)RhCl2Rh(CO)2 (II) with nu(CO) = 2092 and 2022 cm , delta( TC) = 178.7 ppm, and J(CRh) = 75.2 Hz forms when x less than or equal to 0.5. When x > 0.5, the pentacoordinate monocarbonyl complex (cod) CORhCl2RhCO(cod)(III) with nu(CO) = 2050 cm , which is stable in the presence of cod, forms. When x greater than or equal to 3, III is the main product present in the reaction mixtures. In the spectra of such mixtures the TC signal is a singlet with delta( TC) = 178.4 ppm. The butadienecarbonyl complex ((RhCOCl)2C4H6)/sub n/ behaves similarly to I. The reaction involving the replacement of CO ligands by cod in (Rh(CO)2)Cl)2 in a chloroform medium with cod;Rh = 1 passes through a step involving the formation of III; when the reaction is conducted in heptane, the formation of III is not detected.
- OSTI ID:
- 6294789
- Journal Information:
- Sov. J. Coordinat. Chem.; (United States), Journal Name: Sov. J. Coordinat. Chem.; (United States) Vol. 12:6; ISSN SJCCD
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ALKANES
ALKENES
BUTADIENE
CARBON 13
CARBON ISOTOPES
CARBONYLS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMICAL SHIFT
CHLORIDES
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINE COMPOUNDS
CHLOROFORM
COMPLEXES
COMPLEXOMETRY
DEUTERATION
DEUTERIUM COMPOUNDS
DIENES
ETHYLENE
EVEN-ODD NUCLEI
HALIDES
HALOGEN COMPOUNDS
HALOGENATED ALIPHATIC HYDROCARBONS
HEPTANE
HYDROCARBONS
HYDROGEN 1
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFRARED SPECTRA
ISOTOPES
KINETICS
LABELLED COMPOUNDS
LIGANDS
LIGHT NUCLEI
NMR SPECTRA
NUCLEI
ODD-EVEN NUCLEI
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
POLYENES
REACTION KINETICS
REFRACTORY METAL COMPOUNDS
RHODIUM CHLORIDES
RHODIUM COMPLEXES
RHODIUM COMPOUNDS
SPECTRA
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS