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/]
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), Vol. 108:4
- Country of Publication:
- United States
- Language:
- English
Similar Records
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)
Synthesis and properties of nickel(I) and Nickel(II) complexes of a series of macrocyclic N{sub 4} ligands: Crystal structures of C-RSSR-[Ni{sup I}HTIM](ClO{sub 4}), C-RSSR-[Ni{sup II}HTIM](ClO{sub 4}){sub 2}, C-RRSS-[Ni{sup II}HTIM](ClO{sub 4}){sub 2}, and [Ni{sup II}TIM](ClO{sub 4}){sub 2} (HTIM = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradecane, TIM = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene)
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
NICKEL COMPLEXES
OXIDATION
ORGANIC BROMINE COMPOUNDS
REDUCTION
ORGANIC CHLORINE COMPOUNDS
ORGANIC IODINE COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PEROXIDES
ABSORPTION SPECTROSCOPY
ELECTRON TRANSFER
EXPERIMENTAL DATA
RADICALS
VISIBLE SPECTRA
CHEMICAL REACTIONS
COMPLEXES
DATA
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OXYGEN COMPOUNDS
SPECTRA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)