In:
Asian Journal of Organic Chemistry, Wiley, Vol. 6, No. 4 ( 2017-04), p. 458-468
Abstract:
Photoinduced electron transfer (PET) followed by back electron transfer (BET) reactions of 1,2‐bis(α‐styryl)benzenes 1 , generates o ‐quinodimethane derivative 2 via the corresponding radical cation 2 ⋅ + . This process serves as a facile method to form o ‐quinodimethane intermediates. The intermediacy of 2 ⋅ + and 2 were confirmed by using various spectroscopic methods and trapping reactions with 3 O 2 and dienophiles. Kinetic analysis using nanosecond time‐resolved absorption showed that 2 ⋅ + was transformed to 2 via a BET process, in which the decay of 2 ⋅ + and rise of 2 have almost the same rate constants of k DECAY =5.6×10 5 s −1 and k RISE =5.9×10 5 s −1 , respectively. The net BET rate constant evaluated by using Marcus theory is much faster than these experimental values, owing to the reduction based on diffusion.
Type of Medium:
Online Resource
ISSN:
2193-5807
,
2193-5815
DOI:
10.1002/ajoc.201600570
Language:
English
Publisher:
Wiley
Publication Date:
2017
detail.hit.zdb_id:
2679333-7
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