TY - JOUR
T1 - Unusually long lifetimes of the singlet nitrenes derived from 4-azido-2,3,5,6-tetrafluorobenzamides
AU - Marcinek, Andrzej
AU - Platz, Matthew S.
AU - Chan, Stephen Y.
AU - Floresca, Rey
AU - Rajagopalan, Krishnan
AU - Golinski, Miroslaw
AU - Watt, David
PY - 1994
Y1 - 1994
N2 - Laser flash photolysis (308 nm, 20 ns, 150 mJ) of 4-azido-2,3,5,6-tetrafluorobenzamides, esters, and thioesters generates singlet nitrenes which can be intercepted with pyridine to produce strongly absorbing ylides. It was possible to resolve the rate of formation of the ylides as a function of pyridine concentration. This has led to direct measurements of the absolute rate constants of (a) the reaction of the nitrene with pyridine, (b) ring expansion of the nitrene to a ketenimine, and (c) singlet to triplet nitrene intersystem crossing.
AB - Laser flash photolysis (308 nm, 20 ns, 150 mJ) of 4-azido-2,3,5,6-tetrafluorobenzamides, esters, and thioesters generates singlet nitrenes which can be intercepted with pyridine to produce strongly absorbing ylides. It was possible to resolve the rate of formation of the ylides as a function of pyridine concentration. This has led to direct measurements of the absolute rate constants of (a) the reaction of the nitrene with pyridine, (b) ring expansion of the nitrene to a ketenimine, and (c) singlet to triplet nitrene intersystem crossing.
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U2 - 10.1021/j100053a012
DO - 10.1021/j100053a012
M3 - Article
AN - SCOPUS:0001035085
VL - 98
SP - 412
EP - 419
IS - 2
ER -