The Metaphosphite (PO2−) Anion as a Ligand. Issue 52 (25th October 2020)

• Record Type: Journal Article
• Authors: Abbenseth, Josh; Wätjen, Florian; Finger, Markus; Schneider, Sven
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 52(2020)
• Page Start: 23574
• Page End: 23578
• Publication Date: 2020-10-25
• Subjects: metaphosphite -- oxygen atom transfer -- phosphorous -- pincer complex -- rhenium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202011750
• Languages: English
• ISSNs: 1433-7851

Abstract

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. Abstract : Oxygenation of a terminal phosphide complex allowed the synthesis of rhenium(I–III) complexes with the unknown metaphosphite (PO2 − ) ligand. Spectroscopic, crystallographic, and computational examinations revealed slightly stronger σ‐donating and comparable π‐accepting properties as compared to the archetypal nitrite ligand.