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Mechanistic investigation of carbon-carbon bond formation in the reduction of alkyl halides by organonickel complexes in aqueous solution. [R'X (R' = CH/sub 3/, C/sub 2/H/sub 5/, 1-C /sub 3/H/sub 7/, 2-C/sub 3/H/sub 7/, and PhCH/sub 2/; X = Cl, Br, I) RNi(tmc)/sup +/ (R = C/sub 2/H/sub 5/, C/sub 3/H/sub 7/, and CH/sub 2/-c-C/sub 5/H/sub 9/; tmc = (1R,4R,8S,11S)-1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)]

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00264a024· OSTI ID:5826953
;

The macrocyclic alkylnickel(II) complexes, RNi(tmc)/sup +/ (R = C/sub 2/H/sub 5/, C/sub 3/H/sub 7/, and CH/sub 2/-c-C/sub 5/H/sub 9/; tmc = (1R,4R,8S,11S)-1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), react with alkyl halides R'X (R' = CH/sub 3/, C/sub 2/H/sub 5/, 1-C/sub 3/H/sub 7/, 2-C/sub 3/H/sub 7/, and PhCH/sub 2/) 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' = C/sub 2/H/sub 5/, the product distribution compares with that determined 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 C/sub 2/H/sub 5/ + 2-C/sub 3/H/sub 7/I ..-->.. 2-C/sub 3/H/sub 7/ + C/sub 2/H/sub 5/I in aqueous solution was determined by competition with V(H/sub 2/O)/sub 6//sup 2 +/. The value k/sub 2-PrI/ approx. 6 x 10/sup 5/ M/sup -1/ s/sup -1/ is significantly higher than in aprotic solvents. 50 references, 2 figures, 3 tables.

Research Organization:
Iowa State Univ., Ames
DOE Contract Number:
W-7405-ENG-82
OSTI ID:
5826953
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:4; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical &amp; Physicochemical Properties-- (-1987)
AQUEOUS SOLUTIONS
BINDING ENERGY
CATALYSIS
CATALYTIC EFFECTS
CHEMICAL BONDS
CHEMICAL REACTIONS
COMPLEXES
DATA
DISPERSIONS
ENERGY
EXPERIMENTAL DATA
INFORMATION
MIXTURES
NICKEL COMPLEXES
NUMERICAL DATA
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC IODINE COMPOUNDS
ORGANOMETALLIC COMPOUNDS
REDUCTION
SOLUTIONS
TRANSITION ELEMENT COMPLEXES