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Title: The fate of the tert-butyl radical in low-temperature autoignition reactions

 [1]; ORCiD logo [1];  [1]
  1. Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, USA
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Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 19; Related Information: CHORUS Timestamp: 2018-02-14 21:54:48; Journal ID: ISSN 0021-9606
American Institute of Physics
Country of Publication:
United States

Citation Formats

Moore, III, Kevin B., Turney, Justin M., and Schaefer, III, Henry F.. The fate of the tert-butyl radical in low-temperature autoignition reactions. United States: N. p., 2017. Web. doi:10.1063/1.4983128.
Moore, III, Kevin B., Turney, Justin M., & Schaefer, III, Henry F.. The fate of the tert-butyl radical in low-temperature autoignition reactions. United States. doi:10.1063/1.4983128.
Moore, III, Kevin B., Turney, Justin M., and Schaefer, III, Henry F.. 2017. "The fate of the tert-butyl radical in low-temperature autoignition reactions". United States. doi:10.1063/1.4983128.
title = {The fate of the tert-butyl radical in low-temperature autoignition reactions},
author = {Moore, III, Kevin B. and Turney, Justin M. and Schaefer, III, Henry F.},
abstractNote = {},
doi = {10.1063/1.4983128},
journal = {Journal of Chemical Physics},
number = 19,
volume = 146,
place = {United States},
year = 2017,
month = 5

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on May 17, 2018
Publisher's Accepted Manuscript

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  • Techniques for the measurement of bromine leaving group kinetic isotope effects (KIE) are described. Experimental values at 20/sup 0/C for the solvolysis of tert-butyl bromide (0.045 M) in methanol with 0.3 M 2,6-lutidine and for the reaction of n-butyl bromide (0.047 M) with thiophenoxide anion (0.052 M) in 0.25 M lithium methoxide/methanol solvent are 1.003 10 (+-0.000 04) and 1.00l 69 (+-0.000 03), respectively. The natural logarithm of the KIE was found to vary linearly with l/T from 0 to 40/sup 0/C for tert-butyl bromide, slope = 0.472 (+-0.080) deg/sup -1/, and from -10 to 40/sup 0/C for n-butyl bromide,more » slope = 0.531 (+-0.029) deg/sup -1/. The significance of the KIE temperature dependencies is discussed. 6 tables.« less
  • The pulse radiolysis technique was used to generate the alkoxyl radical derived from tert-butyl hydroperoxide (/sup t/BuOOH) in aqueous solution. The reactions of this radical with 2,2'-azinobis(3-ethyl-6-benzothiazolinesulfonate) (ABTS) and promethazine were monitored by kinetic spectroscopy. The unimolecular decay rate constant of the tert-butoxyl radical (/sup t/BuO) was determined to be 1.4 x 10/sup 6/ s/sup -1/. On the basis of this value, the rate constants for /sup t/BuO attack on quercetin, crocin, crocetin, ascorbate, isoascorbate, trolox c, glutathione, thymidine, adenosine, guanosine, and unsaturated fatty acids were determined. In addition, the reaction of /sup t/BuO with the polyunsaturated fatty acids (PUFA)more » was observed by directly monitoring the formation of the fatty acid pentadienyl radicals. Interestingly, the attack of /sup t/BuO on PUFA was found to be faster by about one order of magnitude as compared to the same reaction in a nonpolar solvent.« less
  • Absolute values for the rate constants of the metathesis reactions of DX (X = Br, I) with tert-butyl, generated by 351-nm photolysis of 2,2{prime}-azoisobutane, were determined in a low-pressure Knudsen cell reactor using the VLP{Phi} (very low pressure photolysis) technique. For X = Br, the values are 10{sup {minus}8}k (M{sup {minus}1} s{sup {minus}1}) = 0.9 and 2.3, and for X = I the values are 2.1 and 3.1 at 295 and 384 K. The latter are in good agreement with earlier measurements from this laboratory. The former values are lower by a factor of 50 compared to those recently reportedmore » at 295 K and fail to show the negative activation energy found in that work. Correcting by {radical}2 for the primary isotope effect and combining with the rate constants for the reverse reactions lead to {Delta}H{sub f}{degree} {sub 298}(tert-butyl) (kcal mol{sup {minus}1}) = 9.2 {plus minus}0.5 in both cases. First-order heterogeneous loss of tert-butyl radicals on the Teflon-coated surface employed is small (< 2 s{sup {minus}}1). 17 refs., 9 figs., 3 tabs.« less
  • 1H-1-Oxo-2,4,6,8-tetrakis(tert-butyl)phenoxazine undergoes ligand exchange reactions and behaves as a spin trap for metal-centered radicals, as a result of which stable paramagnetic complexes are formed with delocalization of the unpaired electron in the organic ligand. Paramagnetic complexes are also formed as the result of a reaction between potassium salt (IA) and triphenyl-tin and triphenyl-lead monochlorides.
  • The thorium or uranium metallacycles ((Me/sub 2/Si)/sub 2/N)/sub 2/MCH/sub 2/Si(Me)/sub 2/NSiMe/sub 3/ (I) react with tert-butyl cyanide to give the six-membered ring compounds ((Me/sub 3/Si)/sub 2/N)/sub 2/MN = C(t-Bu)CH/sub 2/Si(Me)/sub 2/NSiMe/sub 3/. The metallacycles (I) also react with the isoelectronic molecules tert-butyl isocyanide and carbon monoxide to give the unique five-membered ring compounds with exocyclic carbon-carbon double bonds, ((Me/sub 3/Si)/sub 2/N)/sub 2/MXC(=CH/sub 2/)Si(Me)/sub 2/NSiMe/sub 3/, where X is t-BuN or oxygen. The four-membered ring metallacycles (I) give simple coordination complexes of the type ((Me/sub 3/Si)/sub 2/N)/sub 2/MCH/sub 2/Si-(Me)/sub 2/NSiMe/sub 3/(N/sub 3/SiMe/sub 3/) with trimethylsilyl azide.