Issue 32, 2024

Analysis of bonding motifs in unusual molecules I: planar hexacoordinated carbon atoms

Abstract

The bonding structures of CO3Li3+ and CS3Li3+ are studied by means of oriented quasi-atomic orbitals (QUAOs) to assess the possibility of these molecules being planar hexacoordinated carbon (phC) systems. CH3Li and CO32− are employed as reference molecules. It is found that the introduction of Li+ ions into the molecular environment of carbonate has a greater effect on the orbital structure of the O atoms than it does on the C atom. Partial charges computed from QUAO populations imply repulsion between the positively charged C and Li atoms in CO3Li3+. Upon the transition from CO3Li3+ to CS3Li3+, the analysis reveals that the substitution of O atoms by S atoms inverts the polarity of the carbon–chalcogen σ bond. This is linked to the difference in s- and p-fractions of the QUAOs of C and S, as element electronegativities do not explain the observed polarity of the CSσ bond. Partial charges indicate that the larger electron population on the C atom in CS3Li3+ makes C–Li attraction possible. Upon comparison with the C–Li bond in methyllithium, it is found that the C–Li covalent interactions in CO3Li3+ and CS3Li3+ have about 14% and 6% of the strength of the C–Li covalent interaction in CH3Li, respectively. Consequently, it is concluded that only CS3Li3+ may be considered to be a phC system.

Graphical abstract: Analysis of bonding motifs in unusual molecules I: planar hexacoordinated carbon atoms

Supplementary files

Article information

Article type
Paper
Submitted
30 Apr 2024
Accepted
19 Jul 2024
First published
23 Jul 2024
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2024,26, 21395-21406

Analysis of bonding motifs in unusual molecules I: planar hexacoordinated carbon atoms

D. Del Angel Cruz, K. N. Ferreras, T. Harville, G. Schoendorff and M. S. Gordon, Phys. Chem. Chem. Phys., 2024, 26, 21395 DOI: 10.1039/D4CP01800A

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