O- vs. N-protonation of 1-dimethylaminonaphthalene-8-ketones: formation of a peri N–C bond or a hydrogen bond to the pi-electron density of a carbonyl group

Mercadal, N., Day, S.P., Jarmyn, A., Pitak, M.B., Coles, S.J., Wilson, C., Rees, G.J., Hanna, J.V. and Wallis, J.D. ORCID: 0000-0001-7259-8783, 2014. O- vs. N-protonation of 1-dimethylaminonaphthalene-8-ketones: formation of a peri N–C bond or a hydrogen bond to the pi-electron density of a carbonyl group. CrystEngComm, 16 (36), pp. 8363-8374. ISSN 1466-8033

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Abstract

X-ray crystallography and solid-state NMR measurements show that protonation of a series of 1-dimethylaminonaphthalene-8-ketones leads either to O protonation with formation of a long N–C bond (1.637–1.669 Å) between peri groups, or to N protonation and formation of a hydrogen bond to the π surface of the carbonyl group, the latter occurring for the larger ketone groups (C(O)R, R = t-butyl and phenyl). Solid state 15N MAS NMR studies clearly differentiate the two series, with the former yielding significantly more deshielded resonances. This is accurately corroborated by DFT calculation of the relevant chemical shift parameters. In the parent ketones X-ray crystallography shows that the nitrogen lone pair is directed towards the carbonyl group in all cases.

Item Type: Journal article
Publication Title: CrystEngComm
Creators: Mercadal, N., Day, S.P., Jarmyn, A., Pitak, M.B., Coles, S.J., Wilson, C., Rees, G.J., Hanna, J.V. and Wallis, J.D.
Publisher: Royal Society of Chemistry
Place of Publication: Cambridge
Date: 2014
Volume: 16
Number: 36
ISSN: 1466-8033
Identifiers:
NumberType
10.1039/c4ce00981aDOI
Rights: © Royal Society of Chemistry 2014
Divisions: Schools > School of Science and Technology
Depositing User: EPrints Services
Date Added: 09 Oct 2015 09:45
Last Modified: 09 Jun 2017 13:09
URI: http://irep.ntu.ac.uk/id/eprint/2110

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