The Metaphosphite (PO2 - ) Anion as a Ligand.

Abstract

The utilization of monomeric, lower phosphorous oxides and oxoanions, such as metaphosphite (PO2 −), which is the heavier homologue of the common nitrite anion but previously only observed in the gas phase and by matrix isolation, requires new synthetic strategies. Herein, a series of rhenium(I–III) complexes with PO2 − as ligand is reported. Synthetic access was enabled by selective oxygenation of a terminal phosphide complex. Spectroscopic and computational examination revealed slightly stronger σ‐donor and comparable π‐acceptor properties of PO2 − compared to homologous NO2 −, which is one of the archetypal ligands in coordination chemistry.