Carbon‐Phosphorus Ligands with Extreme Donating Character

Abstract

AbstractCarbeniophosphines [R2C+−PR2] and phosphonium ylides [R3P+−CR2−] are two complementary classes of carbon‐phosphorus based ligands defined by their unique donor properties. Indeed, while carbeniophosphines are electron‐poor P‐ligands due to the positioning of a positive charge near the coordinating P‐atom, phosphonium ylides are electron‐rich C‐ligands due to the presence of a negatively charged coordinating C‐atom. Based on this knowledge, this account summarizes our recent contribution on these two classes of carbon‐phosphorus ligands, and in particular the strategies developed to lower the donor character of carbeniophosphines and enhance that of phosphonium ylides. This led us to design, at both extremities of the donating scale, extremely electron‐poor P‐ligands exemplified by imidazoliophosphonites [R2C+−P(OR)2] and dicarbeniophosphines [(R2C+)2−PR], and extremely electron‐rich C‐ligands illustrated by pincer architectures exhibiting several phosphonium ylide donor extremities. In the context of carbon‐phosphorus analogy, the closely related cases of ligands where the C‐atom of a NHC ligand is in close proximity of two positive charges, and that of a phosphonium ylide coordinated through its P‐atom are also discussed. An overview of the synthetic methods, coordinating properties, general reactivity and electronic structure of all these C,P‐based species is presented here.