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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...
Autores principales: | , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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Royal Society of Chemistry
2018
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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. |
format | Online Article Text |
id | pubmed-6346288 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
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
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title_full | Relative orientation of the carbonyl groups determines the nature of orbital interactions in carbonyl–carbonyl short contacts
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title_fullStr | Relative orientation of the carbonyl groups determines the nature of orbital interactions in carbonyl–carbonyl short contacts
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title_full_unstemmed | Relative orientation of the carbonyl groups determines the nature of orbital interactions in carbonyl–carbonyl short contacts
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title_short | Relative orientation of the carbonyl groups determines the nature of orbital interactions in carbonyl–carbonyl short contacts
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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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