Carbon-carbon bond formation in the reaction of aliphatic radicals with alkylcobaloximes

Journal Article · Wed Sep 17 04:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00279a037· OSTI ID:5241129

McHatton, R C; Espenson, J H; Bakac, A

Benzyl, methyl, ethyl, and isopropylaquocobaloximes, R'Co(dmgH)/sub 2/OH/sub 2/, react with aliphatic free radicals, R/sup ./, forming RR' and Co/sup II/(dmgH)/sub 2/OH/sub 2/. This reaction is quite general for aliphatic radicals, except for R = benzyl. Rate constants with R = /sup ./C(CH/sub 3/)/sub 2/OH and /sup ./CH(CH/sub 3/)OC/sub 2/H/sub 5/ exhibit little sensitivity toward the steric bulk of substituents on the ..cap alpha..-carbon atom of the organocobaloxime. This discounts homolytic displacement by attack at the organic group. It is proposed that the radical addition takes place at the nitrogen end of the N=C bond of the macrocycle cis to the Co-C bond, followed by the reductive elimination of RR'.

• Research Organization: Iowa State Univ., Ames
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 5241129
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:19; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
AMINES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COBALT COMPOUNDS
DATA
EXPERIMENTAL DATA
HYDROXY COMPOUNDS
INFORMATION
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIMES
RADICALS
REACTION INTERMEDIATES
REACTION KINETICS
TRANSITION ELEMENT COMPOUNDS