Effect of coordination with rhodium on the selectivity of the mass spectral fragmentation of 4,4-disubstituted 2,5-cyclohexadien-1-ones
A comparative study was carried out on the electron impact fragmentation of 4,4-disubstituted 1-oxo-2,5-cyclohexadienes and their rhodium acetylacetonate complexes. The coordination of the diene ligands with rhodium leads to an increase in the selectivity of the decomposition of the molecular ions, which occurs exclusively with loss of the most stable radical located at the geminal unit of the hydrocarbon ..pi..-ligand and leads to (4-methyl-1-oxocyclohexadienyl)acetylacetonatorhodium cations. 15-, 16-, 17-, and 18-Electron complexes containing 4,4-dialkyl-1-oxo-2,5-cyclohexadiene (L) or 4-methyl-1-oxocyclohexadienyl ligands are obtained in the reaction of (acacRh x (CO)/sub n/)/sup +/ and ((C/sub 5/H/sub 5/)Rh(CO)/sub n/)/sup +/ ions (n = 0-2) with 4,4-disubstituted 1-oxo-2,5-cyclohexadienes in the gas phase. The formation of (acacRh(CO)L)/sup +/ and ((C/sub 5/H/sub 5/)Rh(CO)L)/sup +/ ions indicated the reduced ..pi..-donor capacity of 1-oxo-2,5-cyclohexadienes relative to 1-alkylidene-2,5-cyclohexadienes in reactions with rhodium-containing cations.
- Research Organization:
- A.N. Nesmeyanov Institute of Heteroorganic Compounds, Moscow, USSR
- OSTI ID:
- 6476568
- Journal Information:
- Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States), Journal Name: Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States) Vol. 35:5; ISSN BACCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ACETYLACETONE
BINDING ENERGY
CATALYTIC EFFECTS
CATIONS
CHARGED PARTICLES
CHELATING AGENTS
COLLISIONS
COMPLEXES
COMPLEXOMETRY
COORDINATION VALENCES
DIENES
DISSOCIATION
ELECTRON COLLISIONS
ELECTRON-MOLECULE COLLISIONS
ELECTRONIC STRUCTURE
ELECTRONS
ELEMENTARY PARTICLES
ENERGY
FERMIONS
HYDROCARBONS
ION COLLISIONS
ION-MOLECULE COLLISIONS
IONIZATION
IONS
KETONES
LEPTONS
LIGANDS
MASS SPECTRA
MOLECULAR IONS
MOLECULAR STRUCTURE
MOLECULE COLLISIONS
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
POLYENES
REAGENTS
RHODIUM COMPLEXES
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VALENCE