Kinetics and mechanism of the alkylnickel formation in one-electron reductions of alkyl halides and hydroperoxides by a macrocyclic nickel(I) complex. [Ni(IR, 4R 8S, 11S - tmc)/sup +/; tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; and R = CH/sub 3/, C/sub 2/H/sub 5/, C/sub 3/H/sub 7/, or CH/sub 2/CH(CH/sub 2/)/sub 3/ CH/sub 2/ + c - C/sub 5/H/sub 9/CH/sub 2/]

Bakac, A; Espenson, J H

doi:10.1021/ja00264a023

Kinetics and mechanism of the alkylnickel formation in one-electron reductions of alkyl halides and hydroperoxides by a macrocyclic nickel(I) complex. [Ni(IR, 4R 8S, 11S - tmc)/sup +/; tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; and R = CH/sub 3/, C/sub 2/H/sub 5/, C/sub 3/H/sub 7/, or CH/sub 2/CH(CH/sub 2/)/sub 3/ CH/sub 2/ + c - C/sub 5/H/sub 9/CH/sub 2/]

Journal Article · Tue Feb 18 23:00:00 EST 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00264a023· OSTI ID:5815379

Bakac, A; Espenson, J H

The nickel(I) macrocycle Ni(1R,4R,8S,11S-tmc)/sup +/ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) reacts readily with primary alkyl halides in alkaline aqueous solutions, yielding alkylnickel(II) complexes, RNi(tmc)/sup +/. The reaction is proposed to occur in two steps, the first and rate-limiting being one-electron transfer from Ni(tmc)/sup +/ to RX, either by halogen atom transfer or outer-sphere electron transfer, to yield an alkyl radical R. The latter is captured by Ni(tmc)/sup +/ in a second and more rapid reaction. Free radicals are also involved in the formation of alkylnickel complexes in reactions of Ni(tmc)/sup +/ with alkyl hydroperoxides. 53 references, 5 figures, 4 tables.

Research Organization:: Iowa State Univ., Ames

DOE Contract Number:: W-7405-ENG-82

OSTI ID:: 5815379

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

Similar Records

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 · Tue Feb 18 23:00:00 EST 1986 · J. Am. Chem. Soc.; (United States) · OSTI ID:5826953

High electrocatalytic activity of RRSS-[Ni{sup II}HTIM](ClO{sub 4}){sub 2} and [Ni{sup II}DMC](ClO{sub 4}){sub 2} for carbon dioxide reduction (HTIM = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradecane, DMC = C-meso-5,12-dimethyl-1,4,8,11-tetraazacyclotetradecane)

Journal Article · Wed Oct 12 00:00:00 EDT 1994 · Inorganic Chemistry · OSTI ID:421003

Free-radical pathways to alkyl complexes of a nickel tetraaza macrocycle

Journal Article · Wed Aug 27 00:00:00 EDT 1986 · Inorg. Chem.; (United States) · OSTI ID:5058053

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ABSORPTION SPECTROSCOPY
CHEMICAL REACTIONS
COMPLEXES
DATA
ELECTRON TRANSFER
EXPERIMENTAL DATA
INFORMATION
NICKEL COMPLEXES
NUMERICAL DATA
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC IODINE COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDATION
OXYGEN COMPOUNDS
PEROXIDES
RADICALS
REDUCTION
SPECTRA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
VISIBLE SPECTRA

Citation Formats

Similar Records

Related Subjects