Mapping of N-C bond formation from a series of crystalline peri-substituted naphthalenes by charge density and solid-state NMR methodologies
Mapping of N-C bond formation from a series of crystalline peri-substituted naphthalenes by charge density and solid-state NMR methodologies
A combination of charge density studies and solid state nuclear magnetic resonance (NMR)
1J
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
1J
NC couplings of ≈3–6 Hz for long C−N bonds (1.60–1.65 Å), and
1J
NC couplings of <1 Hz for N⋅⋅⋅C >2.1 Å.
NMR spectroscopy, X-ray diffraction, bond theory, through-bond interaction, through-space interaction
23878-23884
Rees, Gregory J.
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Pitak, Mateusz
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Lari, Alberth
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Day, Stephen P.
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Yates, Jonathan R.
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Gierth, Peter
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Barnsley, Kristian
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Smith, Mark
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Coles, Simon J.
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Hanna, John V.
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Wallis, John D.
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25 October 2021
Rees, Gregory J.
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Pitak, Mateusz
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Lari, Alberth
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Day, Stephen P.
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Yates, Jonathan R.
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Gierth, Peter
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Barnsley, Kristian
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Smith, Mark
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Coles, Simon J.
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Hanna, John V.
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Wallis, John D.
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Rees, Gregory J., Pitak, Mateusz, Lari, Alberth, Day, Stephen P., Yates, Jonathan R., Gierth, Peter, Barnsley, Kristian, Smith, Mark, Coles, Simon J., 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 International Edition, 60 (44), .
(doi:10.1002/anie.202111100).
Abstract
A combination of charge density studies and solid state nuclear magnetic resonance (NMR)
1J
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
1J
NC couplings of ≈3–6 Hz for long C−N bonds (1.60–1.65 Å), and
1J
NC couplings of <1 Hz for N⋅⋅⋅C >2.1 Å.
Text
anie.202111100
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Accepted/In Press date: 31 August 2021
e-pub ahead of print date: 31 August 2021
Published date: 25 October 2021
Additional Information:
Funding Information:
We thank the EPSRC for a grant from their Physical Sciences Initiative (EP/E018203/1) (JW/MES), for support of the EPSRC UK National Mass Spectrometry Facility at Swansea University, and for support for the EPSRC National Crystallography Service (SJC). J.V.H. acknowledges the funding of the solid state NMR instrumentation in Millburn House from the EPSRC, the University of Warwick and the Birmingham Science City Advanced Materials Projects 1 and 2 and support by Advantage West Midlands and the European Regional Development Fund. J.V.H. also acknowledges the University of Warwick Scientific Computing Research Technology Platform (RTP), and EPSRC grant EP/K000128/1, for access to the TINUS and MINERVA high‐performance computing clusters. We thank Prof. C. S. Frampton and Dr. L. H. Straver (Bruker Ltd) for collecting an X‐ray dataset, and we thank Dr. Claire Wilson for support in the collection and processing of X‐ray diffraction data at the Diamond Light Source.
Publisher Copyright:
© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.
Keywords:
NMR spectroscopy, X-ray diffraction, bond theory, through-bond interaction, through-space interaction
Identifiers
Local EPrints ID: 451693
URI: http://eprints.soton.ac.uk/id/eprint/451693
ISSN: 1433-7851
PURE UUID: 836d2ca5-ecd8-47a9-8b6e-c307517e8305
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Date deposited: 20 Oct 2021 16:32
Last modified: 17 Mar 2024 02:48
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Contributors
Author:
Gregory J. Rees
Author:
Mateusz Pitak
Author:
Alberth Lari
Author:
Stephen P. Day
Author:
Jonathan R. Yates
Author:
Peter Gierth
Author:
Kristian Barnsley
Author:
Mark Smith
Author:
John V. Hanna
Author:
John D. Wallis
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