Molecular 1,1'-bifunctional mixed-valence P-P compounds, enabled through metal complexation.

Mixed-valence compounds feature the same atoms but in different formal oxidation states. This research field is largely dominated by metal-based solid-state chemistry and has been intensively studied in recent years. By contrast, the situation is different for molecular main group element compounds and to establish 1,1'-bifunctional groups remained a particular challenge. Here a detailed study on 1,1'-bifunctional mixed-valence main group compounds possessing a P-P bond is presented, and the fundamental role of the metal complex fragments is discussed. Based on the generation of a transient phosphanylidene-phosphinidenoid complex a dinuclear diphosphene complex was obtained possessing an unprecedented ambident reactivity, i.e., 1,2-addition or 1,1-addition products were obtained depending on the nature of the reagent. The 1,1-addition products represent stable hitherto unknown 1,1'-bifunctional phosphanylidene-phosphorane complexes which have been confirmed by X-ray diffraction studies. Detailed state-of-the-art DFT calculations provide insight into bonding and reaction pathways.