NDLI: Time-resolved FT-EPR study of photoreduction of duroquinone by triethylamine in methanol

Content Provider	Springer Nature Link
Author	Lu, Jian Ming Beckert, D.
Copyright Year	2000
Abstract	Using time resolved Fourier transform EPR spectroscopy the photoreduction of duroquinone by triethylamine in methanol solution was investigated. It is found that the spin-polarized (CIDEP) duroquinone triplet deactivates by electron transfer from triethylamine generating duroquinone radical anion and amine radical cation, and by hydrogen transfer from the solvent generating durosemiquinone radical and hydroxymethyl radical, respectively. All radicals are observed at different conditions and are spin-polarized by triplet mechanism and partially by ST$_{0}$ radical pair mechanism. The time dependence of FT-EPR intensities of radical cation and radical anion on the amine concentration is investigated in the range of 1 to 100 mM triethylamine. The contribution of the triplet mechanism to the spin polarization of radicals changes with different triethylamine concentrations. The durosemiquinone radical is found to be transformed into duroquinone radical anion in the presence of triethylamine in the solution. CIDNP experiments indicate that the hydrogen back transfer between the durosemiquinone radical and hydroxymethyl radical pair has a significant influence on the time behaviour of duroquinone radical anion. The intensity of triethylamine radical cation is found to be decreased with the increase of triethylamine concentration, which is interpreted that the triethylamine radical cation is deprotonated by the amine. Based on the FT-EPR results, a new complete mechanism is proposed.
Starting Page	621
Ending Page	641
Page Count	21
File Format	PDF
ISSN	09226168
Journal	Research on Chemical Intermediates
Volume Number	26
Issue Number	7-8
e-ISSN	15685675
Language	English
Publisher	Springer Netherlands
Publisher Date	2000-01-01
Publisher Place	Dordrecht
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Catalysis Physical Chemistry Inorganic Chemistry
Content Type	Text
Resource Type	Article
Subject	Chemistry

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