Spin adducts in photolysis of mixed benzoyl phosphonium-iodonium ylides in dichloromethane

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Abstract

Mixed phosphonium-iodonium ylides are of interest as reactants for the synthesis of new heterocyclic compounds. Recently it has been shown that the reactions of the phosphonuim-iodonium ylides under the action of light occurs with the formation of radicals. The radicals generated in the photolysis of the ylide itself and the compounds, which are its fragments, diphenyliodonium salt and triphenylphosphine, as well as participating in its reactions, dichloromethane and phenylacetylene, have been studied with the use of PBN and DMPO spin traps. The obtained results have confirmed the radical mechanism of the photodecomposition of the ylide and allowed to specify the composition of primary radicals generated in the photolysis. The unknown magnetic-resonance parameters for some radicals have been determined.

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About the authors

I. D. Potapov

Emanuel Institute of Biochemical Physics, Russian Academy of Sciences; Moscow State Lomonosov University

Email: nekip@sky.chph.ras.ru
Russian Federation, Moscow; Moscow

M. V. Motyakin

Emanuel Institute of Biochemical Physics, Russian Academy of Sciences

Email: nekip@sky.chph.ras.ru
Russian Federation, Moscow

T. A. Podrugina

Moscow State Lomonosov University

Email: nekip@sky.chph.ras.ru
Russian Federation, Moscow

T. D. Nekipelova

Emanuel Institute of Biochemical Physics, Russian Academy of Sciences

Author for correspondence.
Email: nekip@sky.chph.ras.ru
Russian Federation, Moscow

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Supplementary files

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2. Fig. 1. Experimental (black lines) and theoretical (red lines) EPR spectra of PBN (spectrum 1) and DMPO (spectrum 2) adducts after 4-minute photolysis (λ = 365 nm) of a dichloromethane CH2Cl2 solution at 290 K.

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3. Fig. 2. Experimental (black lines) and theoretical (red lines) EPR spectra of PBN (a) and DMPO (b) spin adducts recorded after 3-min UV irradiation of Ph2I+Cl- in CH2Cl2 at 290 K; (a) – spectra of PBN adducts after irradiation for 0 – (1), 5 – (2), 25 min (3); b – EPR spectrum of DMPO adducts (1) recorded after 3-min photolysis of the solution (EPR lines related to the DMPO/•CH2Cl adduct are marked with asterisks); EPR spectrum of DMPO adducts (2) recorded after 10-min photolysis of the solution.

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4. Fig. 3. Experimental (black lines) and theoretical (red lines) EPR spectra of spin adducts recorded after UV irradiation of a solution of (Ph)3P in CH2Cl2 at 290 K: 1 – spectrum of PBN adducts recorded after 80-second UV irradiation of the solution; 2 – EPR spectrum of DMPO adducts after 120-second UV irradiation of the solution.

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5. Fig. 4. Experimental (black lines) and theoretical (red lines) EPR spectra of PBN (spectrum 1) and DMPO (spectrum 2) adducts recorded after UV irradiation of a solution of phenylacetylene in CH2Cl2 at 290 K.

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6. Fig. 5. Experimental (black lines) and theoretical (red lines) EPR spectra of the adducts PBN (spectrum 1) and DMPO (spectrum 2) after photolysis (λ = 365 nm) of a solution of ylide 1 in CH2Cl2 at 290 K. The inset shows the low-field component of the signal from the DMPO/F• radical, amplified 100-fold.

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7. Scheme 1

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8. 1

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9. Scheme 2

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10. Scheme 3

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11. 2

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12. 3

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13. Scheme 4

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14. Scheme 5

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