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Mapping of N-C bond formation from a series of crystalline peri-substituted naphthalenes by charge density and solid-state NMR methodologies

DOI: 10.1002/anie.202111100 DOI Help

Authors: John D. Wallis (Nottingham Trent University) , Gregory J Rees (University of Oxford) , Mateusz B. Pitak (University of Southampton) , Alberth Lari (Nottingham Trent University) , Stephen P. Day (University of Warwick) , Jonathan R. Yates (University of Oxford) , Peter Gierth (Bruker AXS Ltd) , Kristian Barnsley (University of Warwick) , Mark E. Smith (University of Southampton) , Simon J. Coles (University of Southampton) , John V. Hanna (University of Warwick)
Co-authored by industrial partner: Yes

Type: Journal Paper
Journal: Angewandte Chemie International Edition

State: Published (Approved)
Published: August 2021
Diamond Proposal Number(s): 8521

Open Access Open Access

Abstract: A combination of charge density studies and solid state nuclear magnetic resonance (NMR) 1 J NC 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 sp 2 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 1 J NC couplings of ~2-5 Hz for long C-N bonds (1.60-1.65 Å), and 1 J NC couplings of <1 Hz for N···C > 2.1 Å.

Journal Keywords: Bond Theory; X-ray Diffraction; NMR Spectroscopy; Through-bond interaction; Through-space interaction

Subject Areas: Chemistry, Physics

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 01/09/2021 13:43


Discipline Tags:

Molecular Physics Physics Chemistry Organic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)