Reactions of rhodium(I) carbonyl chloride with olefins

Journal Article · Thu Jan 01 04:00:00 EST 1987 · Sov. J. Coordinat. Chem.; (United States)

OSTI ID:6158718

Varshavskii, Yu S; Kiseleva, N V; Cherkasova, T G; Buzina, N A; Bresler, L S

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), Journal Name: Sov. J. Coordinat. Chem.; (United States) Vol. 12:3; ISSN SJCCD
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
640302 -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ALKENES
BINDING ENERGY
CARBON 13
CARBON ISOTOPES
CARBONYLS
CATALYTIC EFFECTS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
COMPLEXOMETRY
COORDINATION VALENCES
ELECTRONS
ELEMENTARY PARTICLES
ENERGY
EVEN-ODD NUCLEI
FERMIONS
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
HYPERFINE STRUCTURE
INFRARED SPECTRA
INTERMEDIATE MASS NUCLEI
INTERNAL CONVERSION RADIOISOTOPES
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LATTICE VIBRATIONS
LEPTONS
LIGANDS
LIGHT NUCLEI
MAGNETIC RESONANCE
MINUTES LIVING RADIOISOTOPES
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC SOLVENTS
OXIDATION
RADIOISOTOPES
REDUCTION
REFRACTORY METAL COMPOUNDS
RESONANCE
RHODIUM 103
RHODIUM CHLORIDES
RHODIUM COMPLEXES
RHODIUM COMPOUNDS
RHODIUM ISOTOPES
SOLVENT PROPERTIES
SOLVENTS
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
VALENCE
YIELDS