Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules

Fifteen cyclic and acylic carbenes have been calculated with density functional theory at the BP86/def2-TZVPP level. The strength of the internal X→p(π) π-donation of heteroatoms and carbon which are bonded to the C(II) atom is estimated with the help of NBO calculations and with an energy decomposi...

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Autores principales: Andrada, Diego M, Holzmann, Nicole, Hamadi, Thomas, Frenking, Gernot
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2015
Materias:
Full Research Paper
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4734353/
https://www.ncbi.nlm.nih.gov/pubmed/26877795
http://dx.doi.org/10.3762/bjoc.11.294
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author Andrada, Diego M
Holzmann, Nicole
Hamadi, Thomas
Frenking, Gernot
author_facet Andrada, Diego M
Holzmann, Nicole
Hamadi, Thomas
Frenking, Gernot
author_sort Andrada, Diego M
collection PubMed
description Fifteen cyclic and acylic carbenes have been calculated with density functional theory at the BP86/def2-TZVPP level. The strength of the internal X→p(π) π-donation of heteroatoms and carbon which are bonded to the C(II) atom is estimated with the help of NBO calculations and with an energy decomposition analysis. The investigated molecules include N-heterocyclic carbenes (NHCs), the cyclic alkyl(amino)carbene (cAAC), mesoionic carbenes and ylide-stabilized carbenes. The bonding analysis suggests that the carbene centre in cAAC and in diamidocarbene have the weakest X→p(π) π-donation while mesoionic carbenes possess the strongest π-donation.
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spelling pubmed-47343532016-02-12 Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules Andrada, Diego M Holzmann, Nicole Hamadi, Thomas Frenking, Gernot Beilstein J Org Chem Full Research Paper Fifteen cyclic and acylic carbenes have been calculated with density functional theory at the BP86/def2-TZVPP level. The strength of the internal X→p(π) π-donation of heteroatoms and carbon which are bonded to the C(II) atom is estimated with the help of NBO calculations and with an energy decomposition analysis. The investigated molecules include N-heterocyclic carbenes (NHCs), the cyclic alkyl(amino)carbene (cAAC), mesoionic carbenes and ylide-stabilized carbenes. The bonding analysis suggests that the carbene centre in cAAC and in diamidocarbene have the weakest X→p(π) π-donation while mesoionic carbenes possess the strongest π-donation. Beilstein-Institut 2015-12-24 /pmc/articles/PMC4734353/ /pubmed/26877795 http://dx.doi.org/10.3762/bjoc.11.294 Text en Copyright © 2015, Andrada et al. https://creativecommons.org/licenses/by/2.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms)
spellingShingle Full Research Paper
Andrada, Diego M
Holzmann, Nicole
Hamadi, Thomas
Frenking, Gernot
Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules
title Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules
title_full Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules
title_fullStr Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules
title_full_unstemmed Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules
title_short Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules
title_sort direct estimate of the internal π-donation to the carbene centre within n-heterocyclic carbenes and related molecules
topic Full Research Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4734353/
https://www.ncbi.nlm.nih.gov/pubmed/26877795
http://dx.doi.org/10.3762/bjoc.11.294
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