Pincer-supported metal/main-group bonds as platforms for cooperative transformations.

Electron-rich late metals and electropositive main-group elements (metals and metalloids) can be combined to provide an ambiphilic façade for exploring metal-ligand cooperation, yet the instability of the metal/main-group bond frequently limits the study and application of such units. Incorporating main-group donors into pincer frameworks, where they are stabilized and held in proximity to the transition-metal partner, can allow discovery of new modes of reactivity and incorporation into catalytic processes. This Perspective summarizes common modes of cooperativity that have been demonstrated for pincer frameworks featuring metal/main-group bonds, highlighting similarities among boron, aluminium, and silicon donors and identifying directions for further development.