Rate constants of the reactions of Re(CO)/sub 5/ radicals with organic halides determined using ESR spectroscopy

Journal Article · Mon Nov 10 04:00:00 EST 1986 · Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States)

DOI:https://doi.org/10.1007/BF00955353· OSTI ID:6357639

Gasanov, R G; Sadykhov, E G; Freidlina, R Kh

An ESR spectroscopic study was carried out at 20/sup 0/C on the photochemically initiated reaction of Re/sub 2/(CO)/sub 10/ with monohalo and polyhalo aliphatic and aromatic compounds. In substitution reactions involving breakage of a C-Hal bond, Re(CO)/sub 5/ is more than three orders of magnitude more active than CpW(CO)/sub 3/ and more than two or three orders less reactive than Si(C/sub 2/H/sub 5/)/sub 3/ radicals. The rate constants for halogen abstraction by Re(CO)/sub 5/ radicals increase by two orders of magnitude in going from the chlorides to the analogous bromides and from monohaloalkanes to allyl halides and then to benzyl halides and from ..cap alpha..,..cap alpha..-dichloroalkanes to ..cap alpha..,..cap alpha..,..cap alpha..-trichloroalkanes. Comparison of the rate constants for halogen abstraction by Si(C/sub 2/H/sub 5/)/sub 3/ and Re(CO)/sub 5/ radicals yields an explanation for the high efficiency of the Re/sub 2/(CO)/sub 10/ + HSi(C/sub 2/H/sub 5/)/sub 3/ system relative to Re/sub 2/(CO)/sub 10/ alone for the generation of ..cap alpha..-chloro radicals.

• Research Organization: A.N. Nesmeyanov Institute of Heteroorganic Compounds, Moscow, USSR
• OSTI ID: 6357639
• 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

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ADDUCTS
ALKYL RADICALS
ALLYL RADICALS
ANGULAR MOMENTUM
AROMATICS
ARYL RADICALS
BROMINATED ALIPHATIC HYDROCARBONS
BROMINATED AROMATIC HYDROCARBONS
CARBONYLS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINATED AROMATIC HYDROCARBONS
COMPARATIVE EVALUATIONS
COMPLEXES
DECOMPOSITION
DEHYDROGENATION
ELECTRON SPIN RESONANCE
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENATED AROMATIC HYDROCARBONS
HYDRIDES
HYDROGEN COMPOUNDS
KINETICS
MAGNETIC RESONANCE
NITROXYL RADICALS
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC SILICON COMPOUNDS
PARTICLE PROPERTIES
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADICALS
REACTION KINETICS
RESONANCE
RHENIUM COMPLEXES
SILANES
SILICON COMPLEXES
SILICON COMPOUNDS
SPECTRA
SPIN
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES