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, SP, Jarmyn, A, Pitak, MB, Coles, SJ, Wilson, C, Rees, GJ, Hanna, JV and Wallis, JD ORCID: https://orcid.org/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

Preview

Text 219566_PubSub1957_Wallis.pdf Download (3MB) | Preview

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:	Number Type 10.1039/c4ce00981a DOI
Rights:	© Royal Society of Chemistry 2014
Divisions:	Schools > School of Science and Technology
Record created by:	EPrints Services
Date Added:	09 Oct 2015 09:45
Last Modified:	09 Jun 2017 13:09
URI:	https://irep.ntu.ac.uk/id/eprint/2110

Actions (login required)

Edit View

Statistics

Views

Downloads