Experimental and theoretical characterization of the 3,5-didehydrobenzoate anion: A negatively charged meta-benzyne

Jason M. Price, Katrina Emilia Nizzi, J. Larry Campbell, Hilkka I. Kenttämaa, Mark Seierstad, Christopher J. Cramer

Research output: Contribution to journalArticle

11 Scopus citations

Abstract

A negatively charged analogue of meta-benzyne, 3,5-didehydrobenzoate, was synthesized in a Fourier transform ion cyclotron resonance mass spectrometer, and its reactivity was compared to that of the same ion generated previously in a flowing afterglow apparatus and to its positively charged cousin, N-(3,5-didehydrophenyl)-3-fluoropyridinium. 3,5-Didehydrobenzoate was found to react as a nucleophile with electrophilic reagents. In contrast, N-(3,5-didehydrophenyl)-3-fluoropyridinium does not react with the same electrophilic reagents but reacts instead with nucleophilic reagents. Neither ion is able to abstract hydrogen atoms from typical hydrogen atom donors. The absence of any radical reactivity for these metabenzynes is consistent with predictions that radical reactions of singlet biradicals should be hindered as compared to their monoradical counterparts. High-level calculations predict that the carboxylate moiety does not significantly perturb the singlet-triplet splitting of 3,5-didehydrobenzoate relative to the parent meta-benzyne.

Original languageEnglish (US)
Pages (from-to)131-140
Number of pages10
JournalJournal of the American Chemical Society
Volume125
Issue number1
DOIs
StatePublished - Jan 8 2003

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