Oxidation of diamagnetic octa-µ3-chloro-octahedro-hexamolybdenum(II) and -tungsten(II) clusters to paramagnetic dodeca-µ2-chloro-octahedro-hexamolybdenum(3+) and -tungsten(III) clusters

Abstract

Oxidation of tungsten dichloride, [W₆Cl₈, Cl₄, with octachlorocyclopentene at 270 °C yields tungsten trichloride, W₆Cl₁₂]Cl₆. This complex is paramagnetic, containing two unpaired electrons. Similar oxidation of molybdenum dichloride, [Mo₆Cl₈]Cl₄, yields [Mo₆Cl₁₂]Cl₃ in which the average oxidation state of molybdenum is +2·5. The salt (Et₄N)₃[(Mo₆Cl₁₂) Cl₆] is also readily obtained.