Journal of the American Chemical Society p. 719 - 723 (1986)
Update date:2022-08-04
Topics:
Bakac, Andreja
Espenson, James H.
The macrocyclic alkylnickel(II) complexes, RNi(tmc)+ (R = C2H5, C3H7, and CH2-c-C5H9; tmc = (1R,4R,8S,11S)-1,4,8,11-tetramethyl-1,4,8.11-tetraazacyclotetradecane), react with alkyl halides R'X (R'= CH3, C2H5, 1-C3H7, 2-C3H7, and PhCH2) in alkaline aqueous solutions, yielding combination and disproportionation products of R and R'.The reactivity of R'X increases in the order methyl < primary < secondary and Cl < Br < I.In the case R = R' = C2H5, the product distribution compares with that deternined independently for ethyl radicals in aqueous solution.The proposed one-electron reduction of alkyl halide by the alkylnickel complexes in the rate-determining step produces an organonickel(III) complex and the alkyl halide radical anion.Both products rapidly eliminate ethyl radicals whose self-reactions yield the final products.Alkyl halide/alkyl radical exchange reactions effectively compete with radical self-reactions.The rate constant for the reaction C2H5. + 2-C3H7I -> 2-C3H7. + C2H5I in aqueous solution was determined by competition with V(H2O)62+.The value k2-PrI ca. 6E5 M-1s-1 is significantly higher than in aprotic solvents.
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