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

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.