Carbon’s Three-Center-Four-Electron Tetrel Bond, Treated Experimentally
Karim, A., Schulz, N., Andersson, H., Nekoueishahraki, B., Carlsson, A.-C., Sarabi, D., . . . Erdélyi, M. (2018). Carbon’s Three-Center-Four-Electron Tetrel Bond, Treated Experimentally. Journal of the American Chemical Society, 140 (50), 17571-17579. doi:10.1021/jacs.8b09367
Published inJournal of the American Chemical Society
© 2018 American Chemical Society
Tetrel bonding is the noncovalent interaction of group IV elements with electron donors. It is a weak, directional interaction that resembles hydrogen and halogen bonding yet remains barely explored. Herein, we present an experimental investigation of the carbon-centered, three-center, four-electron tetrel bond, [N−C− N]+ , formed by capturing a carbenium ion with a bidentate Lewis base. NMRspectroscopic, titration-calorimetric, and reaction-kinetic evidence for the existence and structure of this species is reported. The studied interaction is by far the strongest tetrel bond reported so far and is discussed in comparison with the analogous halogen bond. The necessity of the involvement of a bidentate Lewis base in its formation is demonstrated by providing spectroscopic and crystallographic evidence that a monodentate Lewis base induces a reaction rather than stabilizing the tetrel bond complex. A vastly decreased Lewis basicity of the bidentate ligand or reduced Lewis acidity of the carbenium ion weakensor even prohibitsthe formation of the tetrel bond complex, whereas synthetic modifications facilitating attractive orbital overlaps promote it. As the geometry of the complex resembles the SN2 transition state, it provides a model system for the investigation of fundamental reaction mechanisms and chemical bonding theories. ...