Reduction of rhenates(VII) with hydrogen chloride in alcohols: The structural aspects of the trans-tetrachloridomethoxidooxidorhenate(VI) products

• Products of the reaction of rhenates(VII) with hydrogen chloride in methanol were isolated.
• No trans influence of the short Re–O bond in trans-tetrachloridomethoxidooxidorhenate(VI) anion is observed.
• EPR and magnetic properties studies confirm the Re(VI) oxidation state.
• DFT studies are presented for trans-tetrachloridoalkoxidooxidorhenate(VI) anions.

A series of phosphonium trans-tetrachloridomethoxidooxidorhenates(VI) was isolated as primary products of the reaction of rhenate(VII) anions with hydrogen chloride in alcohols. The complex [ReOCl4(OCH3)]− anion structure is investigated in detail. It is shown, that in the [ReOCl4(OCH3)]− anion no trans influence of the formally “triple” Re–O bond is present as a result of the “ligands competition effect”. Additionally, quantum-chemical investigations were performed to elucidate the steric and electronic influence of different alkoxido substituents.

Products of the reaction of rhenates(VII) with hydrogen chloride in methanol are investigated, in particular with respect to their structural aspects.Figure optionsDownload as PowerPoint slide