Diphosphines

Diphosphines, sometimes called bisphosphanes, are organophosphorus compounds most commonly used as bidentate phosphine ligands in inorganic and organometallic chemistry. They are identified by the presence of two phosphino groups linked by a backbone, and are usually chelating. A wide variety of diphosphines have been synthesized with different linkers and R-groups. Alteration of the linker and R-groups alters the electronic and steric properties of the ligands which can result in different coordination geometries and catalytic behavior in homogeneous catalysts. Diphosphines, sometimes called bisphosphanes, are organophosphorus compounds most commonly used as bidentate phosphine ligands in inorganic and organometallic chemistry. They are identified by the presence of two phosphino groups linked by a backbone, and are usually chelating. A wide variety of diphosphines have been synthesized with different linkers and R-groups. Alteration of the linker and R-groups alters the electronic and steric properties of the ligands which can result in different coordination geometries and catalytic behavior in homogeneous catalysts. Many widely used diphosphine ligands have the general formula Ar2P(CH2)nPAr2. These compounds can be prepared from the reaction of X(CH2)nX (X=halogen) and MPPh2 (M = alkali metal): Diphosphine ligands can also be prepared from dilithiated reagents and chlorophosphines: This approach is suitable for installing two dialkylphosphino groups, using reagents such as chlorodiisopropylphosphine. Another popular method, suitable for preparing unsymmetrical diphosphines, involves the addition of secondary phosphines to vinylphosphines: (2-Lithiophenyl)diphenylphosphine can be used also to give unsymmetrical diphosphines. The lithiated reagent is available from (2-bromophenyl)diphenylphosphine: The short-chain diphosphine dppm tends to promote metal-metal interactions as illustrated by A-frame complexes. When the two phosphine substituents are linked by two to four carbon centres, the resulting ligands often chelate rings with a single metal. A common diphosphine ligand is dppe, which forms a five-membered chelate ring with most metals. Some diphosphines, such as the extraordinary case of tBu2P(CH2)10PtBu2, give macrocyclic complexes with as many as 72 atoms in a ring. To position phosphine donor groups trans on a coordination sphere, several atoms are required to link the donor centres and long-chain diphosphines are typically floppy and do not chelate well. This challenge has been resolved by the long but rigid diphosphine SPANphos. The bite angle of the diphosphine influences the reactivity of the metal center.