Oxidative Coupling of Terminal Rhenium Pnictide Complexes

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 c...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-08, Vol.58 (32), p.10966-10970
Main Authors: Abbenseth, Josh, Diefenbach, Martin, Hinz, Alexander, Alig, Lukas, Würtele, Christian, Goicoechea, Jose M., Holthausen, Max C., Schneider, Sven
Format: Article
Language:English
Subjects:
Arsenic
Arsenides
Computer applications
Coupling
Crystallography
dipnictides
Group 5A compounds
Ligands
Oxidation
Phosphides
pincer complexes
pnictides
Pyrazole
QTAIM
Rhenium
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Summary: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. 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.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201905130