57 / 2023-08-15 01:11:10

The First Geometrically Distorted Square Pyramidal Phosphoranide

Main group chemistry,phosphorus,distorted geometry,phosphoranide

Phosphorus in Synthetic Chemistry > 1) Phosphorus compounds as catalysts

Geometrical distortion of main group elements leading to a change in the reactivity of these main group centers have recently become an important tool in the main group chemistry. A lot of focus in using this modern method is dedicated to group 15 elements and especially to phosphorus. In this work, we present the synthesis, isolation and preliminary reactivity study of the geometrically distorted, square pyramidal (SP) phosphoranide anion (1⁻). Unlike, trigonal bipyramidal (TBP) phosphoranides that react as nucleophiles, 1⁻ reacts mostly as a strong reductant. One electron oxidation of 1⁻ leads to P−P dimer (1-1) that is formed via the dimerization of unstable SP phosphoranyl radical (1^•), an unprecedented decay pathway for phosphoranyl radicals. Reaction of 1⁻ with benzophenone leads via single electron transfer (SET) to 1-OK and corresponding oxirane.