Stabilizing low-valent refractory metals in a strongly oxidizing medium: The first molybdenum(V) sulfate-MoO(HSO_4)(SO_4)-from Mo(CO)_6 in oleum

摘要

The reaction of Mo(CO)_6 and oleum (65 % SO_3) in a sealed glass tube at 200 °C leads to blue single crystals of MoO(HSO _4)(SO_4). The [MoO] moieties are linked by the [SO _4]~(2-) and [HSO4]- tetrahedra to form double layers that are stacked along the [100] direction (see figure). Strong hydrogen bonding is observed between the two different anions. The thermal decomposition of the compound leads, in a two-step process, to a mixture of MoO_2 and Mo_4O_(11).