Cubic and doubly-fused cubic samarium clusters from Sm(II)-mediated reduction of organic azides and azobenzenes

A polynuclear samarium imido complex [(L)Sm(4)(mu(3)-NSiMe(3))(4)] (2) featuring a cubane-like cluster has been synthesized from the reaction of an organic azide and a samarium(II) complex [(L)SmI(2)Li(2)(THF)(Et(2)O)(2)] (1). In addition, this divalent samarium starting material (1) reacts with azobenzene to give the first example of a well-defined doubly-fused cubic imido-cluster [(L)Sm(6)(mu(3)-NPh)(4)(mu(4)-NPh)(2)I(2)(THF)(2)] (4) in addition to a major cubic complex [(L)Sm(4)(mu(3)-NPh)(4)] (3)