In search for a hydride‐carbene bond

Abstract

AbstractBy presenting a large group of dimers featuring hydride‐carbene bond between silane and various carbenes, we show that electrophilic properties of singlet carbenes can manifest also to a hydridic, ie, negatively charged, hydrogen atom of a hydride. This type of interaction is traced by the corresponding bond path in 18 cases. However, taking into account the fact that in the case of large interatomic distances, the electrostatic potential maps are better indicators of dominant intermolecular interactions, it is shown that the amount of dimers with the hydride‐carbene bond is even larger, as indicated by both the proximity and correct orientation of the π‐hole on the carbene carbon atom and the negative surface of the hydridic hydrogen of the silane molecule. The hydride‐carbene bond is weak, especially when compared with the hydride‐triel bond also involving the silane. In contrast to the latter, the intermolecular charge transfer is negligible. Moreover, the local electrostatic interaction involving the carbene carbon's π‐hole is not necessarily predominant in stabilization of all the carbene⋯silane complexes.