Document Type
Article
Journal/Book Title
The Journal of Physical Chemistry
Publication Date
2-21-2018
Publisher
American Chemical Society
Volume
122
Issue
9
First Page
2550
Last Page
2562
Abstract
The tetravalent character of tetrel atoms leaves only limited room for an incoming nucleophile to approach and engage in a noncovalent bond with a tetrel atom. Any such approach can only occur at the expense of internal geometric distortions. The balance between attractive forces and repulsive steric crowding was studied for a series of Lewis acids of the type FTR3 (T = Si, Ge, Sn, Pb) which were allowed to interact with various bases. The strength and other properties of the tetrel bond are examined as the R groups are made progressively larger, varying from H and CH3 to isopropyl and tert-butyl, which induce steric crowding with the incoming base. The effects of crowding which impede the bond can be offset by enlarging the T atom, by adding electron-withdrawing substituents to the Lewis acid, or by considering stronger bases such as anions. The tetrel bond energies reach up to 10 kcal/mol for a pair of neutral molecules with no electron-withdrawing substituents on the Lewis acid. Adding −CF3 substituents grows the interaction energy to as high as 35 kcal/mol, and a further increment occurs for an anionic base, taking the maximum up to 54 kcal/mol.
Recommended Citation
Scheiner, Steve, "Steric Crowding in Tetrel Bonds" (2018). Chemistry and Biochemistry Faculty Publications. Paper 752.
https://digitalcommons.usu.edu/chem_facpub/752
