Reactions of the spiro monoanion [{(Me2N)Sb(μ-NCy)2}2Sb]− with alcohols and thiols (REH; E = O or S); syntheses of nido-[Sb3(μ-NCy)3(μ3-NCy)(ER)2] anions and the unique antimony(III) imido cubane [(2-NC5H4O)Sb(μ3-NCy)]4 (Cy= cyclohexyl)

Reactions of Sb(NMe2)(3) with a mixture of CyNH2 and (Pr2NM)-N-i (1:1:1 equivalents) afforded a simple route to M[{(Me2N)Sb(mu-NCy)(2)}(2)Sb] (M = Li 1 . Li or Na 1 . Na), containing the spiro anion [{(Me2N)Sb(mu-NCy)(2)}(2)Sb](-) 1. The reactions of 1 . Li with (BuOH)-Bu-t/(BuOK)-Bu-t and with 2-HS{1-Me(imid)} (imid = imidazole) (2 equivalents) gave [K .eta(6)-C6H5Me][Sb-3(mu-NCy)(3)(mu(3)-NCy)((OBu)-Bu-t)(2)] 2 and Li[Sb-3(mu-NCy)(3)(mu(3)-NCy)(S{2-Me(imid)})(2)] 3, respectively, in which the spiro structure of the precursor rearranges into a nido framework. Reaction of 1 . Li with HOC5H4N-2 led to disintegration of the Sb3N6 anion core and formation of the unique antimony(III) imido cubane [(2-NC5H4O)Sb(mu(3)-NCy)](4) 4. The crystal structures of the new complexes 1 . Na, 3 and 4 were determined.