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Relative orientation of the carbonyl groups determines the nature of orbital interactions in carbonyl–carbonyl short contacts

Carbonyl–carbonyl (CO···CO) interactions are emerging noncovalent interactions found in many small molecules, polyesters, peptides and proteins. However, little is known about the effect of the relative orientation of the two carbonyl groups on the nature of these interactions. Herein, we first show...

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Detalles Bibliográficos
Autores principales: Sahariah, Biswajit, Sarma, Bani Kanta
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6346288/
https://www.ncbi.nlm.nih.gov/pubmed/30774885
http://dx.doi.org/10.1039/c8sc04221g
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author Sahariah, Biswajit
Sarma, Bani Kanta
author_facet Sahariah, Biswajit
Sarma, Bani Kanta
author_sort Sahariah, Biswajit
collection PubMed
description Carbonyl–carbonyl (CO···CO) interactions are emerging noncovalent interactions found in many small molecules, polyesters, peptides and proteins. However, little is known about the effect of the relative orientation of the two carbonyl groups on the nature of these interactions. Herein, we first show that simple homodimers of acetone and formaldehyde can serve as models to understand the effect of relative orientations of the two carbonyl groups on the nature of CO···CO interactions. Further, from a comprehensive statistical analysis of molecules having inter- or intramolecular CO···CO interactions, we show that the molecules can be broadly categorized into six different structural motifs (I–VI). The analysis of pyramidality of the acceptor carbon atoms in these motifs and natural bond orbital (NBO) analysis suggest that the relative orientation of the two interacting carbonyl groups determines whether the orbital interaction between the two carbonyl groups would be n → π* or π → π* or a combination of both.
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spelling pubmed-63462882019-02-15 Relative orientation of the carbonyl groups determines the nature of orbital interactions in carbonyl–carbonyl short contacts Sahariah, Biswajit Sarma, Bani Kanta Chem Sci Chemistry Carbonyl–carbonyl (CO···CO) interactions are emerging noncovalent interactions found in many small molecules, polyesters, peptides and proteins. However, little is known about the effect of the relative orientation of the two carbonyl groups on the nature of these interactions. Herein, we first show that simple homodimers of acetone and formaldehyde can serve as models to understand the effect of relative orientations of the two carbonyl groups on the nature of CO···CO interactions. Further, from a comprehensive statistical analysis of molecules having inter- or intramolecular CO···CO interactions, we show that the molecules can be broadly categorized into six different structural motifs (I–VI). The analysis of pyramidality of the acceptor carbon atoms in these motifs and natural bond orbital (NBO) analysis suggest that the relative orientation of the two interacting carbonyl groups determines whether the orbital interaction between the two carbonyl groups would be n → π* or π → π* or a combination of both. Royal Society of Chemistry 2018-10-29 /pmc/articles/PMC6346288/ /pubmed/30774885 http://dx.doi.org/10.1039/c8sc04221g Text en This journal is © The Royal Society of Chemistry 2019 https://creativecommons.org/licenses/by-nc/3.0/This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)
spellingShingle Chemistry
Sahariah, Biswajit
Sarma, Bani Kanta
Relative orientation of the carbonyl groups determines the nature of orbital interactions in carbonyl–carbonyl short contacts
title Relative orientation of the carbonyl groups determines the nature of orbital interactions in carbonyl–carbonyl short contacts
title_full Relative orientation of the carbonyl groups determines the nature of orbital interactions in carbonyl–carbonyl short contacts
title_fullStr Relative orientation of the carbonyl groups determines the nature of orbital interactions in carbonyl–carbonyl short contacts
title_full_unstemmed Relative orientation of the carbonyl groups determines the nature of orbital interactions in carbonyl–carbonyl short contacts
title_short Relative orientation of the carbonyl groups determines the nature of orbital interactions in carbonyl–carbonyl short contacts
title_sort relative orientation of the carbonyl groups determines the nature of orbital interactions in carbonyl–carbonyl short contacts
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6346288/
https://www.ncbi.nlm.nih.gov/pubmed/30774885
http://dx.doi.org/10.1039/c8sc04221g
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