Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume 2019, Issue 47, Pages 4974-4984Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201901092
Keywords
Rhenium; Selenolates; Tellurolates; Schiff bases; Reduction
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Funding
- German Academic Exchange Service (DAAD, Germany)
- Coordenadoria de Aperfeicoamento de Pessoal de Nivel Superior (CAPES, Brazil)
- DFG
- High-Performance-Computing (HPC) Centre of the Zentraleinrichtung fur Datenverarbeitung (ZEDAT) of the Freie Universitat Berlin
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The salicylidene Schiff bases of bis(2-aminophenyl)diselenide and -ditelluride react with [ReOCl3(PPh3)(2)] or the arylimidorhenium(V) compounds [Re(NPhR)Cl-3(PPh3)(2)] (R = H, F, CF3) with formation of rhenium(V) complexes with tridentate {O,N,Se/Te} chalcogenolato ligands. The ligands adopt a facial coordination mode with the oxygen donors trans to the multiply bonded O2- or NPhR2- ligands. The reduction of the dichalcogenides and the formation of the chalcogenolato ligands occurs in situ by released PPh3 ligands. The absence of additional reducing agents provides good yields of products with rhenium in the high formal oxidation state +5. A mechanism for the dichalcogenide reduction is proposed on the basis of the experimental results. In accordance with the proposed mechanism, best yields are obtained with a strict exclusion of oxygen, but in the presence of water.
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