Carbenes and phosphonium ylides: a fruitful association in coordination chemistry

Among a plethora of σ-donor ligands available, carbon-centered ones have become essential, in particular with the emergence of N-heterocyclic carbenes (NHCs), positioning themselves as credible alternatives to traditional nitrogen- and phosphorus-based systems. Phosphonium ylides representing another class of neutral η¹-bonded carbon ligands have also been shown to act as effective Lewis bases. Considering the intrinsic features of the carbene and phosphonium ylide ligands, similar in terms of electronic properties, but different in terms of bonding mode, the design of hybrid systems combining these two types of carbon functionalities appeared to be a natural and exciting challenge. This Perspective comprehensively covers the chemistry of such ligand architectures from synthesis and fundamental aspects to catalytic applications.