Ambident phosphinomethanide ligands: From robust complexes to fragile frameworks

The ambidentate nature of phosphinomethanides leads to a broad variety of coordination modes to metal centers. For instance, high phosphine coordination numbers are achieved with diphosphinomethanide ligands. Furthermore, phosphinomethanides undergo readily rearrangements on reaction with electrophiles, leading to a manifold of new compounds with unexpected structural features, e.g. novel heterocycles. In addition, redox reactions with oxidative coupling of the phosphinomethanides are often encountered, which again lead to novel heterocyclic structures with group 15 element oxidants like PCl₃ or AsCl₃.