Journal of Physical Chemistry p. 3714 - 3721 (1982)
Update date:2022-08-11
Topics:
Andrews, Lester
Kelsall, Benuel J.
Payne, Christopher K.
Rodig, Oscar R.
Schwarz, Helmut
Matrix photoionization of chlorocycloheptatriene (CCHT) during condensation with excess argon at 20 K produced new broad 484-, 517-, and 544-nm bands, a sharp 469.3-nm absorption, and weak 453- and 468-nm bands.The broad bands are assigned to the 1-, 2-, and 3-chlorocycloheptatriene cations.Photolysis with 500- 1000-nm radiation decreased the broad bands and increased the sharp 469.3-nm absorption.The 469.3-nm band and a sharp 707.8-nm counterpart in benzyl chloride experiments suggest a conjugated triene cation identification with 6-chloro-5-methylene-1,3-cyclohexadiene cation (3) as the most reasonable possibility.The 453- and 468-nm bands, which markedly increased on near-UV photolysis in benzyl chloride experiments, were strong products in similar studies with 7-chloronorbornadiene.Photolysis with 470-1000-nm radiation decreased the 468-nm band and increased the 453-nm absorption; this interconversion was reversed with 370-460-nm radiation.The latter bands are probably due to E and Z isomers of 5-(chloromethylene)-1,3-cyclohexadiene cation (6), which isomerize upon photoexcitation.
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