American Chemical Society, Journal of the American Chemical Society, 40(130), p. 13373-13381, 2008
DOI: 10.1021/ja804010h
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Exchange of organic radicals between solution and organo-cobalt complexes is experimentally observed and the reaction pathway is probed through DFT calculations. Cyanoisopropyl radicals from AIBN (2,2'-azobisisobutyronitrile) enter solutions of cobalt(II) tetramesityl porphyrin ((TMP)Co(II)*, 1) and vinyl acetate (VAc) in benzene and react to produce transient hydride (TMP)Co-H and radicals (*CH(OAc)CH2C(CH3)2CN (R1*)) that proceed on to form organo-cobalt complexes (TMP)Co-CH(OAc)CH3 (4, Co-R2) and (TMP)Co-CH(OAc)CH2C(CH3)2CN (3, Co-R1), respectively. Rate constants for cyanoisopropyl radical addition with vinyl acetate and hydrogen atom transfer to (TMP)Co(II)* are reported through kinetic studies for the formation and transformation of organo-cobalt species in this system. Rate constants for near-degenerate exchanges of radicals in solution with organo-cobalt complexes are deduced from (1)H NMR studies and kinetic modeling. DFT computations revealed formation of an unsymmetrical adduct of (TMP)Co-CH(OAc)CH3 (4) with *CH(OAc)CH3 (R2*) and support an associative pathway for radical interchange through a three-centered three-electron transition state [R...Co...R]. Associative radical interchange of the latent radical groups in organo-cobalt porphyrin complexes with freely diffusing radicals in solution that is observed in this system provides a pathway for mediation of living radical polymerization of vinyl acetate.