Document Type

Article

Journal/Book Title

International Journal of Quantum Chemistry

Publication Date

12-13-2018

Publisher

Wiley

First Page

1

Last Page

18

Abstract

The carbene triel bond is predicted and characterized by theoretical calculations. The C lone pair of N‐heterocyclic carbenes (NHCs) is allowed to interact with the central triel atom of TrR3 (Tr = B and Al; R = H, F, Cl, and Br). The ensuing bond is very strong, with an interaction energy of nearly 90 kcal/mol. Replacement of the C lone pair by that of either N or Si weakens the binding. The bond is strengthened by electron‐withdrawing substituents on the triel atom, and the reverse occurs with substitution on the NHC. However, these effects do not strictly follow the typical pattern of F > Cl > Br. The TrR3 molecule suffers a good deal of geometric deformation, requiring on the order of 30 kcal/mol, in forming the complex. The R(C···Tr) bond is quite short, for example, 1.6 Å for Tr = B, and shows other indications of at least a partially covalent bond, such as a high electron density at the bond critical point and a good deal of intermolecular charge transfer.

Comments

This is the peer reviewed version of the following article: Chi Z, Dong W, Li Q, Yang X, Scheiner S, Liu S. Carbene triel bonds between TrR3 (Tr = B, Al) and N‐heterocyclic carbenes. Int J Quantum Chem. 2018;e25867. https://doi.org/10.1002/qua.25867, which has been published in final form at https://doi.org/10.1002/qua.25867. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.

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