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Time‐resolved infrared studies of triplet 1,3‐cyclopentanediyl
Author(s) -
Showalter Brett M.,
Bentz Timothy C.,
Ryzhkov Lev R.,
Hadad Christopher M.,
Toscano John P.
Publication year - 2000
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/1099-1395(200006)13:6<309::aid-poc242>3.0.co;2-a
Subject(s) - chemistry , photodissociation , photochemistry , acetonitrile , infrared spectroscopy , infrared , kinetics , spectroscopy , oxygen , pentane , triplet state , argon , ring (chemistry) , molecule , organic chemistry , physics , quantum mechanics , optics
Triplet‐sensitized photolysis of 2,3‐diazabicyclo[2.2.1]hept‐2‐ene ( 1 ) in argon‐ or oxygen‐ saturated acetonitrile‐ d 3 solutions results in the formation of bicyclo[2.1.0]pentane ( 3 ), a ring closure product arising from an intermediate 1,3‐cyclopentanediyl triplet biradical ( 2 ). Time‐resolved infrared (TRIR) spectroscopy was used to monitor the kinetics of bicyclopentane 3 production. This analysis provides a measurement of the triplet biradical lifetime and an estimate of the bimolecular reaction rate between biradical 2 and oxygen, both in good agreement with previous investigations. Our studies also indicate that certain IR bands due to 3 in the C–H stretching region overlap with corresponding bands in biradical 2 . This interpretation is supported by computational investigations.Copyright © 2000 John Wiley & Sons, Ltd.