Intermolecular Insertion Reactions into the P−P Bond of Oligophosphorus Compounds

The insertion of unsaturated organic molecules into a P−P bond of oligophosphorus compounds has the potential to expand the organophosphorus and organometallic chemistry and to make it more variable with the selective formation of desirable products. This article reviews the insertion reaction for oligophosphorus compounds and focuses in particular on non‐metals, unsaturated organic substrates, carbenes and carbene analogues as starting reagents. The intermolecular insertion reactions of small molecules into P−P bonds of oligophosphorus compounds are described. This type of reactivity is important for the development of new, targeted and selective methods for the activation of oligophosphorus compounds to obtain new oligophosphorus ligands and materials.