Gas-Phase Reactivity of the 2,6- and 3,5-Dimethylenepyridinium Biradicals

Autor:	Eric D. Nelson, Hilkka I. Kenttämaa, Kami K. Thoen
Rok vydání:	1998
Předmět:	Chemistry Isocyanide General Chemistry Photochemistry Biochemistry Catalysis Fourier transform ion cyclotron resonance Ion Gas phase Reaction rate chemistry.chemical_compound Colloid and Surface Chemistry Reagent Spin trap Reactivity (chemistry)
Zdroj:	Journal of the American Chemical Society. 120:3792-3798
ISSN:	1520-5126 0002-7863
Popis:	The 2,6- and 3,5-dimethylenepyridinium biradical ions were generated and structurally characterized in the gas phase by using Fourier transform ion cyclotron resonance mass spectrometry. Their reactivity was examined toward several commonly used spin traps. Reaction rates and product distributions were determined. The isomeric biradicals were found to possess remarkably different chemical properties. Most importantly, the 2,6-dimethylenepyridinium biradical is highly reactive toward all the reagents studied, while the 3,5-dimethylenepyridinium biradical reacts slowly or not at all. The reaction of the 2,6-dimethylenepyridinium biradical with tert-butyl isocyanide occurs via HCN abstraction and addition, the same pathways observed for isomeric closed-shell pyridylmethyl cations. In contrast, the 3,5-dimethylenepyridinium biradical reacts exclusively by slow addition. The same reaction was observed for the analogous 3-methylenepyridinium monoradical ion. The 3,5-dimethylenepyridinium biradical and the 3-met...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::29835b38b49d9c1c3e81b053be8c4950 https://doi.org/10.1021/ja974159w Zobrazit plný text záznamu