Diphosphines - Chain Length and Coordinating Properties

Chain Length and Coordinating Properties

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. The most common diphosphine ligand is 1,2-Bis(diphenylphosphino)ethane, 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.

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