caa a22 4500 475758323 CHVBK 20180406123543.0 cr unu---uuuuu 170329e20000101xx s 000 0 eng 10.1007/BF02499064 doi (NATIONALLICENCE)springer-10.1007/BF02499064 Laser flash photolysis of fluorinated aryl azides in neutral and acidic solutions [Elektronische Daten] [D. Pol'shakov, Yu. Tsentalovich, N. Gritsan] Laser flash photolysis of perfluoro-4-biphenyl azide andN-propyl-4-azido-2,3,5,6-tetrafluorobenzylamide in acetonitrile, water-acetonitrile mixtures, and HCl-containing solutions was studied. The absorption spectra of primary intermediates, singlet arylnitrenes(2a(S) and2b(S), respectively), were recorded. The absolute rate constants of their intersystem crossing in MeCN were measured, and the corresponding Arrhenius parameters were found from the temperature dependences of the rate constants of isomerization of singlet arylnitrenes2a(S) and2b(S) to azirines. Protonation of singlet arylnitrenes2a(S) and2b(S) was observed, the rate constants of their protonation were measured, and the transient absorption spectra of arylnitrenium ions were recorded. It was shown by quantum-chemical calculations (the hybrid B3LYP method) that the arylnitrenium ions that formed have the singlet ground state and the singlet-triplet gap is ∼20 kcal mol−1. Kluwer Academic/Plenum Publishers, 2000 laser flash photolysis nationallicence aryl azides nationallicence singlet arylnitrenes nationallicence protonation nationallicence arylnitrenium ions nationallicence quantum-chemical calculations nationallicence Pol'shakov D. Novosibirsk State University, 2 ul. Pirogova, 630090, Novosibirsk, Russian Federation aut Tsentalovich Yu International Tomography Center, Siberian Branch of the Russian Academy of Sciences, 3a ul. Institutskaya, 630090, Novosibirsk, Russian Federation aut Gritsan N. Novosibirsk State University, 2 ul. Pirogova, 630090, Novosibirsk, Russian Federation aut Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/1(2000-01-01), 50-55 1066-5285 49:1<50 2000 49 11172 https://doi.org/10.1007/BF02499064 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF02499064 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Pol'shakov D. Novosibirsk State University, 2 ul. Pirogova, 630090, Novosibirsk, Russian Federation aut NATIONALLICENCE 700 1- Tsentalovich Yu International Tomography Center, Siberian Branch of the Russian Academy of Sciences, 3a ul. Institutskaya, 630090, Novosibirsk, Russian Federation aut NATIONALLICENCE 700 1- Gritsan N. Novosibirsk State University, 2 ul. Pirogova, 630090, Novosibirsk, Russian Federation aut NATIONALLICENCE 773 0- Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/1(2000-01-01), 50-55 1066-5285 49:1<50 2000 49 11172 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer