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Price JM, Nizzi KE, Campbell JL, et al. Experimental and theoretical characterization of the 3,5-didehydrobenzoate anion: a negatively charged meta-benzyne. J Am Chem Soc. 2003;125(1):131-40doi: 10.1021/ja021112o.
Price, J. M., Nizzi, K. E., Campbell, J. L., Kenttämaa, H. I., Seierstad, M., & Cramer, C. J. (2003). Experimental and theoretical characterization of the 3,5-didehydrobenzoate anion: a negatively charged meta-benzyne. Journal of the American Chemical Society, 125(1), 131-40. https://doi.org/10.1021/ja021112o
Price, Jason M, et al. "Experimental and theoretical characterization of the 3,5-didehydrobenzoate anion: a negatively charged meta-benzyne." Journal of the American Chemical Society vol. 125,1 (2003): 131-40. doi: https://doi.org/10.1021/ja021112o
Price JM, Nizzi KE, Campbell JL, Kenttämaa HI, Seierstad M, Cramer CJ. Experimental and theoretical characterization of the 3,5-didehydrobenzoate anion: a negatively charged meta-benzyne. J Am Chem Soc. 2003 Jan 08;125(1):131-40. doi: 10.1021/ja021112o. PMID: 12515514.
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J Am Chem Soc. 2003 Jan 08;125(1):131-40. doi: 10.1021/ja021112o.

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

Journal of the American Chemical Society

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

Affiliations

  1. Department of Chemistry, Purdue University, West Lafayette, IN 47907-1393, USA.

PMID: 12515514 DOI: 10.1021/ja021112o

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 meta-benzynes 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.

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