Abstract
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.
Similar content being viewed by others
References
Azides and Nitrenes, Reactivity and Utility, Ed. E. F. V. Scriven, New York, 1984.
G. B. Schuster and M. S. Platz,Adv. Photochem., 1992,17, 69.
N. P. Gritsan and E. A. Pritchina,Usp. Khim., 1992,61, 910 [Russ. Chem. Rev., 1992,61 (Engl. Transl.)].
W. L. Karney and W. T. Borden,J. Am. Chem. Soc., 1997,119, 1378.
W. L. Karney and W. T. Borden,J. Am. Chem. Soc., 1997,119, 3347.
N. P. Gritsan, T. Yuzawa, and M. S. Platz,J. Am. Chem. Soc., 1997,119, 5059.
R. Born, C. Burda, P. Senn, and J. Wirz,J. Am. Chem. Soc., 1997,119, 5061.
N. P. Gritsan, H. B. Zhai, T. Yuzawa, D. Karweik, J. Brooke, and M. S. Platz,J. Phys. Chem. A, 1997,101, 2833.
N. P. Gritsan, E. V. Cherepanova, and M. S. Plats,Optika i Spektroskopiya, 1997,83, 870 [Opt. Spectrosc., 1997,83 (Engl. Transl.)].
K. A. Schnapp, R. Poe, E. Leyva, N. Soudararajan, and M. S. Platz,Bioconjugate Chem., 1993,4, 172.
K. A. Schnapp and M. S. Platz,Bioconjugate Chem., 1993,4, 178.
R. A. McClelland, M. J. Kahley, R. A. Davidse, and G. Hadzialicm,J. Am. Chem. Soc., 1996,118, 4794.
J. Michalak, H. B. Zhai, and M. S. Platz,J. Phys. Chem., 1996,100, 14028.
P. Ramlall and R. A. McClelland,J. Chem. Soc., Perkin Trans. 2, 1999, 225.
R. C. Garner, C. N. Martin, and D. B. Clayson, inChemical Carcinogenesis, 2nd ed., Ed. G. C. Siarle, ACS Monograph Series 1982, ACS, Washington, DC, 19841, 175.
F. M. Rapoport and A. A. Il'inskaya, inLaboratornye metody polucheniya chistykh gazov [Laboratory Methods for Preparation of Pure Goses], Goskhimizdat, Moscow, 1963, 132 (in Russian).
I. F. Molokov, Yu. P. Tsentalovich, A. V. Yurkovskaya, and R. Z. Sagdeev,J. Photochem. Photobiol., A: Chem., 1997,110, 159.
A. D. Becke,J. Chem. Phys., 1993,98, 1372.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, and J. A. Pople,GAUSSIAN94, Gaussian, Inc., Pittsburgh (PA), 1995.
C. J. Cramer and F. J. Dulles,J. Am. Chem. Soc., 1994,116, 9787.
Author information
Authors and Affiliations
Additional information
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 49–54, January, 2000.
Rights and permissions
About this article
Cite this article
Pol'shakov, D.A., Tsentalovich, Y.P. & Gritsan, N.P. Laser flash photolysis of fluorinated aryl azides in neutral and acidic solutions. Russ Chem Bull 49, 50–55 (2000). https://doi.org/10.1007/BF02499064
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF02499064