期刊
CHEMPHYSCHEM
卷 22, 期 19, 页码 1958-1966出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.202100527
关键词
frustrated Lewis pairs; methane activation; density functional calculations; main group chemistry
资金
- University of Namur
- Namur Institute of Structured Matter (NISM)
- Fonds de la Recherche Scientifique-FNRS (F.R.S.-FNRS) [F.4513.18]
- FNRS-FRFC
- Walloon Region
- University of Namur [GEQ U.G006.15, U.G018.19, 1610468, RW/GEQ2016]
The article demonstrates the activation of methane using 1-aza-9-boratriptycene as an intramolecular frustrated Lewis pair (FLP) through density functional theory (DFT) analysis. The study shows that the nature of the Lewis base influences the selectivity over the reaction pathway, with N Lewis bases favoring the deprotonation mechanism and P bases the hydride abstraction one.
The activation or heterolytic splitting of methane, a challenging substrate usually restricted to transition metals, has so far proven elusive in experimental frustrated Lewis pair (FLP) chemistry. In this article, we demonstrate, using density functional theory (DFT), that 1-aza-9-boratriptycene is a conceptually simple intramolecular FLP for the activation of methane. Systematic comparison with other FLP systems allows to gain insight into their reactivity with methane. The thermodynamics and kinetics of methane activation are interpreted by referring to the analysis of the natural charges and by employing the distortion-interaction/activation strain (DIAS) model. These showed that the nature of the Lewis base influences the selectivity over the reaction pathway, with N Lewis bases favoring the deprotonation mechanism and P bases the hydride abstraction one. The lower barrier of activation for 1-aza-9-boratriptycene and the higher products stability are due to a better interaction energy than its counterparts, itself due to electrostatic interactions with the methane moiety, favorable orbital overlaps allowed by the side-attack, and space proximity between the B and N atoms.
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