Interaction between Spirosilanes and Lewis Bases: from Coordination to Frustration

In this work, the interaction between Lewis bases, especially N-heterocyclic carbenes (NHCs), and hindered neutral silicon derivatives featuring high Lewis acidity is described. The formation of normal and abnormal Lewis adducts could be controlled by varying the acidity of the corresponding tetravalent spiro organosilane. Some DFT calculations permitted to gain insight into the thermodynamics of the NHC–spirosilane interaction featuring various NHCs differing in size and σ-donor capacity. Spirosilanes are introduced as new Lewis partners in frustrated Lewis pair (FLP) chemistry and some FLP-type reactivities are presented, in particular the activation of formaldehyde that could occur with both hindered NHCs and phosphines.