Interacting Quantum Atoms Analysis of Covalent and Collective Interactions in Single Elongated Carbon–Carbon Bonds

TL;DR

This paper explores how long carbon-carbon bonds remain stable by analyzing electronic interactions in molecules with bulky substituents.

Contribution

The study reveals the role of collective non-covalent interactions in stabilizing elongated C–C bonds using advanced quantum analysis methods.

Findings

Collective non-covalent interactions dominate over covalent bonding in molecules with bulky substituents.

Electron sharing and London dispersion contribute significantly to the stability of long C–C bonds.

Wave function analysis methods like QTAIM and IQA provide insights into the bonding mechanisms of these molecules.

Abstract

Chemical bonds among carbon atoms are central to chemistry. A general working principle regarding these interactions is that these contacts become stronger as the carbon atoms become closer to each other. Nevertheless, there are long, yet strong single C–C bonds that challenge this interpretation. Herein, we perform a quantitative thorough decomposition of the electronic energy of hexaphenylethane and several derivatives of this molecule with increasingly bulkier substituents. For this purpose, we exploit state-of-the-art methods of wave function analysis for the examination of the chemical bonding scenario in the examined systems, namely, the quantum theory of atoms in molecules (QTAIM) and the interacting quantum atoms (IQA) electronic energy partition. Our results reveal the predominance of collective non-covalent interactions over the central, covalent one in the chemical bonding of the examined molecules, in particular for those that have been synthesized in the laboratory. The QTAIM and IQA methods also showed that, besides London dispersion, electron sharing comprises an important contribution to the abovementioned collective interactions. Overall, our results give valuable insights about the importance of collective interactions in the investigated systems and they aid in the understanding of the nature of long, yet stable single C–C bonds.

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