Whereas sp2 and sp-hybridized carbon compounds have been described as electron-rich species able to interact with electron-deficient moieties to form π and σ-hole bonds, to the best of our knowledge there is no report in the literature of sp3 carbons acting as Lewis bases in hole-bonds. By means of a combined structural and computational analysis we have demonstrated the unexpected ability of alkyl groups to act as electron density donors in π-hole bonding with triel centres. The nature of the interaction is mainly electrostatic for Al and Ga, as evidenced by energy decomposition analysis. There is also some orbital contribution as revealed by a NBO analysis, namely between the σC-H orbitals of the methyl group and an empty orbital of the Group 13 center. The unexpected strength and controllable topology of these alkyl-Lewis base interactions open the possibility to use them as a new tool in crystal design and engineering.

Alkyl groups as electron density donors in π-hole bonding

255th National Meeting (2018)

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