The reaction of [Os6(CO)18] with [(SPPh2)2NH]: Facile rearrangement of the metal framework

The reaction of [Os6(CO)18] 1 with [(SPPh2)2NH] in the presence of Me3NO produces a purple compound characterized spectroscopically and by X-ray crystallography, as [HOs6(CO)17(SPPh2)2N] 2. The structure shows the hexanuclear fragment to have suffered a geometrical rearrangement to give a metal framework that can be described as an edge-bridged tetrahedron with an additional terminal osmium atom bonded to one of the bridged metal atoms. The ligand acts as a bimetallic tetraconnective unit through both sulphur atoms between two non-bonded osmium atoms.