Transient intermediates in the photolysis of iodonium cations
作者:
R. J. Devoe,
M. R. V. Sahyun,
N. Serpone,
D. K. Sharma,
期刊:
Canadian Journal of Chemistry
(NRC Available online 1987)
卷期:
Volume 65,
issue 10
页码: 2342-2349
ISSN:0008-4042
年代: 1987
DOI:10.1139/v87-391
出版商: NRC Research Press
数据来源: NRC
摘要:
Pulsed picosecond laser photolysis of the diphenyliodonium cation indicates that excitation of the allowed transition is followed by rapid (ps) deactivation to a homolytically dissociative state, presumablyT1. Steady-state photolysis yields iodobenzene and biphenyl from the primary radical products. Iodobiphenyl is also observed. We infer in-cage recombination of these radical products, with intervention of a carbocationic intermediate. Laser flash photolysis of diphenyliodonium iodide in its charge transfer band yields an initial transient with a lifetime of ca. 200 ps. A strongly absorbing secondary transient is observed on the nanosecond time scale. Iodobenzene is the exclusive reaction product. We infer that it is not formed directly from the primary photoproduct, but through in-cage recombination of phenyl cation with iodide anion, as in benzenediazonium iodide.
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