Abstract

Upon oxidation by dry oxygen of electrolytes produced by anodic stripping of rhenium in a methanol solution of MoO(OMe)(4) in the presence of the electroconductive LiCl until Re : Mo >= 4 : 1, brown-black crystals separate slowly. The precipitate is unstable in air. Its X-ray powder diffraction pattern is virtually unchangeable, but the rhenium-to-molybdenum ratio is variable and close to the metal ratio in the electrolyte. An X-ray structure experiment on an Re : Mo approximate to 9 : 1 single crystal showed that the crystal is structurally built of tetranuclear, nearly planar molecules M(4)O(6-y)(OMe)(12+y) (M = Re, Mo). The M atoms are bonded through oxo bridges along two opposite sides of the rectangle and pairs of methoxide bridges along the other two sides. The remaining three positions in the coordination sphere of the metal are occupied by two terminal alkoxo groups and the oxygen atom (trans to the alkoxide bridge), which are disordered to positions corresponding to the terminal oxo and alkoxo groups. For all M atoms, the occupancy of the alkoxo group position is smaller than the value calculated according to the assumption that only rhenium(V) (molybdenum(VI)) atoms are present in the structure, which is indicative of the presence of rhenium(VI).

Published in

Russian Journal of Inorganic Chemistry / Zhurnal Neorganicheskoi Khimii
1999, Volume: 44, number: 3, pages: 332-339
Publisher: MAIK NAUKA/INTERPERIODICA/SPRINGER

UKÄ Subject classification

Inorganic Chemistry


Permanent link to this page (URI)

https://res.slu.se/id/publ/50558