Mapping of N-C Bond Formation from a Series of Crystalline Peri-Substituted Naphthalenes by Charge Density and Solid-State NMR Methodologies.
Angew Chem Int Ed Engl
; 60(44): 23878-23884, 2021 Oct 25.
Article
in En
| MEDLINE
| ID: mdl-34464506
ABSTRACT
A combination of charge density studies and solid state nuclear magnetic resonance (NMR) 1 JNC 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 Nâ
â
â
C distance reduces there is a sharp decrease in the Laplacian derived from increasing charge density between the two groups at ca. Nâ
â
â
C = 1.8â
Å, with the periodic DFT calculations predicting, and heteronuclear spin-echo NMR measurements confirming, the 1 JNC couplings of ≈3-6â
Hz for long C-N bonds (1.60-1.65â
Å), and 1 JNC couplings of <1â
Hz for Nâ
â
â
C >2.1â
Å.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Angew Chem Int Ed Engl
Year:
2021
Document type:
Article
Affiliation country:
United kingdom