Issue 3, 2019

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

Abstract

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
22 9 2018
Accepted
27 10 2018
First published
29 10 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2019,10, 909-917

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

B. Sahariah and B. K. Sarma, Chem. Sci., 2019, 10, 909 DOI: 10.1039/C8SC04221G

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