Reactions of rhodium(I) carbonyl chloride with olefins
The reactions of (Rh(CO)/sub 2/Cl)/sub 2/ (Y/sub 0/) with cyclooctene and several other olefins (1-heptene, 1-hexene, ethylene, and cyclohexene) have been studied by IR and /sup 13/C NMR spectroscopy. The main reaction products are the binuclear complexes Rh/sub 2/L(CO)/sub 3/Cl/sub 2/ (Y/sub 1/) and (RhL(CO)Cl)/sub 2/ (Y/sub 2/), where L denotes the olefin. The extent of replacement of the carbonyl groups depends on the nature of the olefin and the conditions under which the reaction is carried out (the L:Rh ratio and the removal of CO from the reaction sphere). The liquid olefins form the following series according to their ability to replace the carbonyl groups: C/sub 8/H/sub 14/ > C/sub 7/H/sub 14/, C/sub 6/H/sub 12/ > C/sub 6/H/sub 10/. In the presence of an excess of C/sub 8/H/sub 14/, Y/sub 2/ disproportionates with the formation of a dicarbonyl product, which presumably corresponds to the formula Rh(C/sub 8/H/sub 14/)/sub 2/(CO)/sub 2/Cl (a pentacoordinate complex with a trigonal-bipyramidal structure). The /sup 13/C signal in the NMR spectrum of a solution of Y/sub 2/ in C/sub 8/H/sub 14/ is a singlet with sigma(/sup 13/C) 180.3 ppm, which is an indication of the rapid exchange of the carbonyl groups. Rapid exchange of the CO ligands is also observed in solutions of Y/sub 0/ in the olefins (with the exception of C/sub 6/H/sub 10/). For example, the /sup 13/C signal in the spectrum of a solution of Y/sub 0/ in C/sub 8/H/sub 14/ is a singlet with sigma(/sup 13/C) 179.8 ppm. The spectrum of Y/sub 0/ in C/sub 6/H/sub 10/ is a doublet with sigma(/sup 13/C) = 178.5 ppm and /sup 1/J(CRh) = 76.3 Hz. A scheme for the interaction of Y/sub 0/ with olefins based on the conception of the trans antagonism of ..pi..-acceptor ligands has been proposed.
- OSTI ID:
- 6158718
- Journal Information:
- Sov. J. Coordinat. Chem.; (United States), Vol. 12:3; Other Information: Translated from Koordinatsionnaya Khimiya; 12: No.3, 355-365(Mar 1986)
- Country of Publication:
- United States
- Language:
- English
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ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
ALKENES
COMPLEXOMETRY
CARBONYLS
RHODIUM COMPLEXES
BINDING ENERGY
CARBON 13
CATALYTIC EFFECTS
CHEMICAL REACTION YIELD
COORDINATION VALENCES
ELECTRONS
HYPERFINE STRUCTURE
INFRARED SPECTRA
LATTICE VIBRATIONS
LIGANDS
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
ORGANIC SOLVENTS
OXIDATION
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RHODIUM 103
RHODIUM CHLORIDES
SOLVENT PROPERTIES
CARBON ISOTOPES
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
ELEMENTARY PARTICLES
ENERGY
EVEN-ODD NUCLEI
FERMIONS
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
INTERMEDIATE MASS NUCLEI
INTERNAL CONVERSION RADIOISOTOPES
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LEPTONS
LIGHT NUCLEI
MAGNETIC RESONANCE
MINUTES LIVING RADIOISOTOPES
NUCLEI
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
RADIOISOTOPES
REFRACTORY METAL COMPOUNDS
RESONANCE
RHODIUM COMPOUNDS
RHODIUM ISOTOPES
SOLVENTS
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
VALENCE
YIELDS
400201* - Chemical & Physicochemical Properties
640302 - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory