Spectral and kinetic measurements on a series of persistent iminoxyl radicals

Autor:	Minghui Wang, G. David Mendenhall, Brian M. Eisenhauer, Maria Ngo, Karl W. Kettinger, Henryk Labaziewicz, Richard E. Brown
Rok vydání:	1997
Předmět:	Chemistry Radical Organic Chemistry Kinetics Kinetic energy Medicinal chemistry Decomposition Spectral line law.invention Reaction rate constant Computational chemistry law Molecular orbital Physical and Theoretical Chemistry Electron paramagnetic resonance
Zdroj:	Journal of Physical Organic Chemistry. 10:737-746
ISSN:	1099-1395 0894-3230
DOI:	10.1002/(sici)1099-1395(199710)10:10<737::aid-poc944>3.0.co;2-n
Popis:	A series of new iminoxyl radicals, Et3C(C=NO·)Bu-tert (1), tert-C5H11(C=NO·) Bu-tert (2), (tert-C5H11)2C=NO· (3), Et3C(C=NO·)Ph (4), PhCH2CMe2(C=NO·)Bu-tert (5), PhCMe2(C=NO·)Bu-tert (6) and Me2CH(C=NO·)C5H11-tert (7), was characterized by EPR and in some cases visible spectra and decay kinetics in solution. Isolation of 1H and 3-tert-butyl-4,4-diethyl-5-methyl-4,5-dihydro-5-isoxazolol (9) among the decomposition products of 1 was consistent with a previously unrecognized mode of iminoxyl reaction in which the initial step is an internal β-H abstraction. Molecular orbital calculations on H2C=NO· indicate a C–N–O angle of about 140° and a 10 kcal mol−1 barrier to inversion. Rate constants for the reaction of tert-Bu2C=NO· (8) with a series of olefins were measured. © 1997 John Wiley & Sons, Ltd.
Databáze:	OpenAIRE
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