Mapping of N−C Bond Formation from a Series of Crystalline Peri‐Substituted Naphthalenes by Charge Density and Solid‐State NMR Methodologies

Rees, Gregory J. and Pitak, Mateusz B. and Lari, Alberth and Day, Stephen P. and Yates, Jonathan R. and Gierth, Peter and Barnsley, Kristian and Smith, Mark E. and Coles, Simon J. and Hanna, John V. and Wallis, John D. (2021) Mapping of N−C Bond Formation from a Series of Crystalline Peri‐Substituted Naphthalenes by Charge Density and Solid‐State NMR Methodologies. Angewandte Chemie, 133 (44). pp. 24071-24077. ISSN 0044-8249

Abstract

AbstractA combination of charge density studies and solid state nuclear magnetic resonance (NMR) 1JNC coupling measurements supported by periodic density functional theory (DFT) calculations is used to characterise the transition from an n–π* interaction to bond formation between a nucleophilic nitrogen atom and an electrophilic sp2 carbon atom in a series of crystalline peri‐substituted naphthalenes. As the N⋅⋅⋅C distance reduces there is a sharp decrease in the Laplacian derived from increasing charge density between the two groups at ca. N⋅⋅⋅C = 1.8 Å, with the periodic DFT calculations predicting, and heteronuclear spin‐echo NMR measurements confirming, the 1JNC couplings of ≈3–6 Hz for long C−N bonds (1.60–1.65 Å), and 1JNC couplings of <1 Hz for N⋅⋅⋅C >2.1 Å.