Oxidative Coupling of Terminal Rhenium Pnictide Complexes. Issue 32 (28th June 2019)

• Record Type: Journal Article
• Authors: Abbenseth, Josh; Diefenbach, Martin; Hinz, Alexander; Alig, Lukas; Würtele, Christian; Goicoechea, Jose M.; Holthausen, Max C.; Schneider, Sven
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 32(2019)
• Page Start: 10966
• Page End: 10970
• Publication Date: 2019-06-28
• Subjects: dipnictides -- pincer complexes -- pnictides -- QTAIM -- rhenium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201905130
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The isolation of rhenium(V) complexes with terminal phosphide and arsenide ligands was achieved upon decarbonylation of rhenium(III) pnictaethynolates. One‐electron oxidation of the pnictide complexes yielded Pn−Pn (Pn=P, As) coupling products, which were spectroscopically and crystallographically characterized. Computational bond analysis suggests that these complexes are best described as {Pn2 } 0 complexes that are stabilized by donor–acceptor interactions with the metal and a pyrazole ligand. Abstract : A radical coupling : The use of a hemilabile ligand that facilitates decarbonylation upon linkage isomerism enabled the synthesis and isolation of terminal rhenium phosphide and arsenide complexes from pnictaethynolate precursors. One‐electron oxidation of the pnictide complexes resulted in intermolecular Pn−Pn coupling, giving side‐on bound P2 and As2 species.