28550-92-7Relevant articles and documents
TEMPO-Mediated Catalysis of the Sterically Hindered Hydrogen Atom Transfer Reaction between (C5Ph5)Cr(CO)3H and a Trityl Radical
Gunasekara, Thilina,Abramo, Graham P.,Hansen, Andreas,Neugebauer, Hagen,Bursch, Markus,Grimme, Stefan,Norton, Jack R.
supporting information, p. 1882 - 1886 (2019/02/14)
We have demonstrated the ability of TEMPO to catalyze H· transfer from (C5Ph5)Cr(CO)3H to a trityl radical (tris(p-tert-butylphenyl)methyl radical). We have measured the rate constant and activation parameters for the direct reaction, and for each step in the catalytic process: H· transfer from (C5Ph5)Cr(CO)3H to TEMPO and H· transfer from TEMPO-H to the trityl radical. We have compared the measured rate constants with the differences in bond strength, and with the changes in the Global Electrophilicity Index determined with high accuracy for each radical using state of the art quantum chemical methods. We conclude that neither is a major factor in determining the rates of these H· transfer reactions and that the effectiveness of TEMPO as a catalyst is largely the result of its relative lack of steric congestion compared to the trityl radical.
Evidence for formation of a Co-H bond from (H2O) 2Co(dmgBF2)2 under H2: Application to radical cyclizations
Li, Gang,Han, Arthur,Pulling, Mary E.,Estes, Deven P.,Norton, Jack R.
, p. 14662 - 14665 (2012/11/07)
Under H2, the radical cyclization of appropriate dienes can be catalyzed by cobaloximes. H can be abstracted from an intermediate (presumably a cobalt hydride) by trityl radicals (Ar3C) or by TEMPO. The rate-determining step in these reactions is the uptake of H2, which is second order in cobalt and first order in hydrogen; the third-order rate constant is 106(3) M-2As-1.
Sterically Hindered Free Radicals, XIX. - Stable 4,4',4''-Trisubstituted Triphenylmethyl Radicals
Duennebacke, Dieter,Neumann, Wilhelm P.,Penenory, Alicia,Stewen, Ulrich
, p. 533 - 536 (2007/10/02)
The title radicals (4-R-C6H4)3C. (1), R = F, Cl, Ph, OMe, NO2, tBu, OEt, SMe, CN, CF3, have been prepared, the latter four for the first time, and the ESR spectra have been recorded. aoH, amH, and as