Aspects of Molybdenum Chemistry in the Basic NaCl / AlCl3 Melt at 175°C

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Abstract
A number of molybdenum chlorides and oxychlorides have been investigated in the sodium tetrachloroaluminate melt. The three‐ and five‐oxidation states were stable in the melt, but the six‐oxidation state, added as , , and , oxidized the melt and was itself reduced to Mo(V). The behavior of this Mo(V) was indistinguishable from that of Mo(V) added directly to the melt as the pentachloride. Mechanisms have been proposed to rationalize the electrochemical oxidation of Mo(III) and reduction of Mo(V), although in the latter case layer formation on the electrode surface prevented a dennitive characterization. A disproportionation mechanism is believed to be operative in the oxidation of Mo(III), and by cyclic voltammetry and rotating ring‐disk techniques it has been possible to detect an intermediate Mo(IV) species.

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