UNUSUALLY LONG LIFETIMES OF THE SINGLET NITRENES DERIVED FROM 4-AZIDO-2,3,5,6-TETRAFLUOROBENZAMIDES

被引：55

作者：

MARCINEK, A

PLATZ, MS

CHAN, SY

FLORESCA, R

RAJAGOPALAN, K

GOLINSKI, M

WATT, D

机构：

[1] OHIO STATE UNIV,DEPT CHEM,COLUMBUS,OH 43210

[2] UNIV KENTUCKY,DEPT CHEM,LEXINGTON,KY 40506

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1994年 / 98卷 / 02期

关键词：

D O I：

10.1021/j100053a012

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页码：412 / 419

页数：8

共 29 条

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