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ESR study of the reaction of cyclopentadienyl complexes of zirconium hydrides with benzyl halides in the presence of 2,4,6-tri-tert-butylnitrosobenzene

Journal Article · · Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States)
DOI:https://doi.org/10.1007/BF00956636· OSTI ID:6476908
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An ESR study was carried out on the reactions of Cp/sub 2/ArH/sub 2/ (A), Cp/sub 2/ZrH(Cl) (B), and Cp/sub 3/ArH (C) (Cp = eta/sup 5/-C/sub 5/H/sub 5/) with benzyl halides in the presence of 2,4,6-tri-tert-butylnitrosobenzene (BNB). The ESR spectrum in the case of the reaction of (C) with BNB in benzene or toluene shows ArN(O)H radicals (Ar = 2,4,6-(Me/sub 3/C)/sub 3/C/sub 6/H/sub 2/) (a/sub H/ = 11.7, a/sub H/ = 13.0, a/sub m-H/ = 1.1 Oe). The ESR spectrum under the same conditions with C/sub 6/H/sub 5/CH/sub 2/Br shows signals for (C/sub 6/H/sub 5/CH/sub 2/N(O)Ar)/sub st/ radicals (I) (C approx. 5 x 10/sup -6/ M, a/sub N/ = 13.6, a/sub ..beta..-H/ = 14.7, a/sub m-H/ = 0.8 Oe). Radicals (I) were also obtained in the reaction of (C) with C/sub 6/H/sub 5/CH/sub 2/Cl in the presence of H, but the yield was only about 10/sup -7/ M. Radicals (I) were also detected by ESR spectroscopy in the reaction of (A) or (B) with C/sub 6/H/sub 5/CH/sub 2/Br. All the reactions were carried out in an inert-gas atmosphere at about 20/sup 0/C in the absence of irradiation. The formation of radicals (I) in the reactions studied may be attributed to the radical abstraction of bromine or chlorine from the benzyl halides.
Research Organization:
N.D. Zelinskii Institute of Organic Chemistry, Moscow, USSR
OSTI ID:
6476908
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. 35:6; ISSN BACCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
AROMATICS
BENZENE
BROMINATED AROMATIC HYDROCARBONS
CATALYTIC EFFECTS
CHEMICAL BONDS
CHLORINATED AROMATIC HYDROCARBONS
COMPLEXES
CYCLOALKENES
CYCLOPENTADIENE
DIENES
DISSOCIATION
ELECTRON SPIN RESONANCE
HALOGENATED AROMATIC HYDROCARBONS
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
MAGNETIC RESONANCE
NITROSO COMPOUNDS
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
POLYENES
RESONANCE
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
ZIRCONIUM COMPLEXES
ZIRCONIUM COMPOUNDS
ZIRCONIUM HYDRIDES