Abstract
The traditional view of phosphines as Lewis bases or ligands in transition metal complexes is challenged by the series of adducts involving phosphorus(III) Lewis acids. A variety of ligands form complexes with the phosphadiazonium cation (Mes*NP + ) or phosphenium cation (Ph 2 P + ). Structural features are compared with related systems to highlight new directions in structure, bonding and reactivity. Complexes involving homoatomic P-P coordinate bonds are susceptible to ligand exchange reactions, a versatile new approach for element-P bond formation. Phosphenium cations can be associated using tethered diphosphine ligands.
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