Reactivity of a σ,σ,σ,σ-tetraradical: the 2,4,6-tridehydropyridine radical cation.
The 2,4,6-tridehydropyridine radical cation, an analogue of the elusive 1,2,3,5-tetradehydrobenzene, was generated in the gas phase and its reactivity examined. Surprisingly, the tetraradical was found not to undergo radical reactions. This behavior is rationalized by resonance structures hindering fast radical reactions. This makes the cation highly electrophilic, and it rapidly reacts with many nucleophiles by quenching the N-C ortho-benzyne moiety, thereby generating a relatively unreactive meta-benzyne analogue.
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
Vanessa A
VA
Gallardo
Bartłomiej J
BJ
Jankiewicz
Nelson R
NR
Vinueza
John J
JJ
Nash
Hilkka I
HI
Kenttämaa
D002412:Cations / Q000138:chemical synthesis / Q000737:chemistry; D005609:Free Radicals / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D011725:Pyridines / Q000138:chemical synthesis / Q000737:chemistry*; D011726:Pyridinium Compounds / Q000138:chemical synthesis / Q000737:chemistry*
D002412:Cations; D005609:Free Radicals; D011725:Pyridines; D011726:Pyridinium Compounds