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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...
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