3474-12-2Relevant articles and documents
Halogen abstraction reaction between aminoalkyl radicals and alkyl halides: Unusual high rate constants
Lalevée,Allonas,Fouassier
scheme or table, p. 415 - 418 (2009/02/02)
The very high reactivity of aminoalkyl radicals toward the halogen abstraction reaction is reported for the first time. Reaction rate constants with CCl4 and CBr4 are close to the diffusion limit: they are about 4-5 orders of magnitude higher than those previously determined for typical alkyl radicals. A better understanding of this unusual behavior is obtained using molecular orbitals (MO) calculations. The participation of polar effects is directly evidenced. This approach can be useful for the design of new reducing agents.
FTIR and computational studies of gas-phase hydrogen atom abstraction kinetics by t-butoxy radical
Li, Shuping,Fan, Wai Yip
, p. 276 - 280 (2007/10/03)
By using Fourier-Transform Infrared (FTIR) absorption spectroscopy, rate coefficients in the range of 10-16 to 10-14 cm3 molecule-1 s-1 have been determined for the hydrogen atom abstraction reactions of several substrates including halogenated organic compounds and amines by t-butoxy radical generated from the uv photolysis of t-butyl nitrite in the gas phase. Arrhenius parameters for selected reactions have been measured in the temperature range 299-318 K. Transition states and activation barriers for such reactions have been computed with the help of Gaussian 03 software and found to match very well with the experimental values.
Reactivity of the radical anion OCC-
Van Doren, Jane M.,Miller, Thomas M.,Stevens Miller, Amy E.,Viggiano,Morris, Robert A.,Paulson, John F.
, p. 7407 - 7414 (2007/10/02)
The characteristic reactivity of the radical anion OCC- has been investigated in the gas phase at 298 K through determination of rate coefficients, products, and branching fractions for each of 29 ion-molecule reactions. A wide variety of reactions is observed including abstraction of H, H+, and H2+, nucleophilic displacement, charge transfer, and reactions involving electron detachment. Many of the reactions involve cleavage of the C--CO bond, consistent with the relatively small C--CO bond energy and the proposed1 electronic structure of the ground state anion in which both radical and charge are centered on the terminal carbon. Similarities are noted between the chemistry of OCC- and its neutral analogue OCC and between the chemistry of OCC- and the radical anions O- and o-C6H4-. Most reaction products observed are consistent with reaction mechanisms involving initial attack of the terminal carbon in OCC- on the neutral reaction partner. The gas-phase acidity of HCCO is bracketed between those of CH3NO2 and CH3CHO, yielding 1502 ± 8 > ΔGoacid(HCCO) ≥ 1463 ± 8 kJ mol-1 and 1531 ± 12 > ΔHoacid(HCCO) ≥ 1491 ± 12 kJ mol-1. Observation of H atom transfer from CH2Cl2 to OCC- indicates that ΔHof(OCC-) ≥ 148 ± 12 kJ mol-1 and gives a larger lower limit of ΔHoacid ≥ 1507 ± 15 kJ mol-1. These and related thermochemical values, including the hydrogen bond dissociation energy in HCCO, are compared with literature values.