The Non-innocent Role of Spin Traps in Monitoring Radical Formation in Copper-Catalyzed Reactions
作者： Mohammad Samanipour , H. Y. Vincent Ching , Hans Sterckx , Bert U. W. Maes , Sabine Van Doorslaer
DOI: 10.1007/S00723-020-01284-0
关键词: Density functional theory 、 Photochemistry 、 Hyperfine structure 、 Radical 、 Electron paramagnetic resonance 、 Solid-state physics 、 Nitrogen 、 Spectroscopy 、 Chemistry 、 Molecule
摘要: Spin traps, like 5,5-dimethyl-1-pyrroline N-oxide (DMPO), are commonly used to identify radicals formed in numerous chemical and biological systems, many of which contain metal-ion complexes. In this study, continuous wave electron paramagnetic resonance hyperfine spectroscopy prove the equatorial ligation DMPO(-derived) molecules Cu(II), even presence competing nitrogen bases. The experimental data corroborated with density functional theory calculations. It is shown that 14N HYSCORE can be as a fingerprint method reveal coordination an interaction might influence outcome spin-trapping experiments consequently conclusion drawn on mechanism under study.
springer.com
sci-hub.st 参考文章(55)
Scott D. McCann, Shannon S. Stahl, Copper-Catalyzed Aerobic Oxidations of Organic Molecules: Pathways for Two-Electron Oxidation with a Four-Electron Oxidant and a One-Electron Redox-Active Catalyst Accounts of Chemical Research. ,vol. 48, pp. 1756- 1766 ,(2015) , 10.1021/ACS.ACCOUNTS.5B00060
Hans Sterckx, Johan De Houwer, Carl Mensch, Ignacio Caretti, Kourosch Abbaspour Tehrani, Wouter A. Herrebout, Sabine Van Doorslaer, Bert U. W. Maes, Mechanism of the CuII-catalyzed benzylic oxygenation of (aryl)(heteroaryl)methanes with oxygen Chemical Science. ,vol. 7, pp. 346- 357 ,(2016) , 10.1039/C5SC03530A
A. Pöppl, M. Hartmann, W. Böhlmann, R. Böttcher, Coordination Geometry of the Copper−Pyridine Complex in Frozen Solution As Studied by Proton and Deuterium Two-Dimensional Hyperfine Sublevel Correlation Electron Spin Resonance Spectroscopy Journal of Physical Chemistry A. ,vol. 102, pp. 3599- 3606 ,(1998) , 10.1021/JP980406M
Sergei A. Dikanov, Andrei P. Spoyalov, Jürgen Hüttermann, Exploiting the properties of line‐shape singularities in orientationally selected electron spin echo envelope modulation spectra of Cu2+−(15N‐imidazole)4 for the determination of hyperfine coupling with the remote imidazole nitrogen Journal of Chemical Physics. ,vol. 100, pp. 7973- 7983 ,(1994) , 10.1063/1.466790
R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions Journal of Chemical Physics. ,vol. 72, pp. 650- 654 ,(1980) , 10.1063/1.438955
Lavrent Khachatryan, Cheri A. McFerrin, Randall W. Hall, Barry Dellinger, Environmentally Persistent Free Radicals (EPFRs). 3. Free versus Bound Hydroxyl Radicals in EPFR Aqueous Solutions Environmental Science & Technology. ,vol. 48, pp. 9220- 9226 ,(2014) , 10.1021/ES501158R
Axel D. Becke, A New Mixing of Hartree-Fock and Local Density-Functional Theories Journal of Chemical Physics. ,vol. 98, pp. 1372- 1377 ,(1993) , 10.1063/1.464304
H. J. Scholl, J. Huettermann, ESR and ENDOR of copper(II) complexes with nitrogen donors: probing parameters for prosthetic group modeling of superoxide dismutase The Journal of Physical Chemistry. ,vol. 96, pp. 9684- 9691 ,(1992) , 10.1021/J100203A023
Phillip M. Hanna, Walee Chamulitrat, Ronald P. Mason, When are metal ion-dependent hydroxyl and alkoxyl radical adducts of 5,5-dimethyl-1-pyrroline N-oxide artifacts? Archives of Biochemistry and Biophysics. ,vol. 296, pp. 640- 644 ,(1992) , 10.1016/0003-9861(92)90620-C
Marcos A. Bizeto, Wendel A. Alves, César A. S. Barbosa, Ana M. D. C. Ferreira, Vera R. L. Constantino, Evaluation of Hexaniobate Nanoscrolls as Support for Immobilization of a Copper Complex Catalyst Inorganic Chemistry. ,vol. 45, pp. 6214- 6221 ,(2006) , 10.1021/IC0600580