Preparative and structural studies on sulfur-linked carborane icosahedra: 2-Phenyl-ortho-carboranyl-sulfur systems (2-Ph-1,2-C2B10H10)2X (X = S, S2 or SO), and ortho-carboran-di-yl systems (1,2-C2B10H10Y)2 (Y = S or SO)

Details are reported of the preparation and X-ray structural characterisation of the new compounds (PhCbo)2X, where PhCbo = 2-Ph-1,2-C2B10H10 and X = S (1) or SO (3), prepared from PhCboLi and SCl2 or SOCl2 respectively, as well as the known compound with X = S2 (2). Hydrogen in the presence of palladium/carbon reduced (3) to (1). Features of their structures (exo C–S and cage C–C distances and substituent orientations) are consistent with significant exo SC dative π-bonding from their sulfur atoms to the cage hypercarbon atoms and weak exo π-bonding from the phenyl groups. Attempts to prepare systems (CboY)2, in which two ortho-carboran-di-yl residues Cbo are linked through two bridging units Y (S, SO) are also reported, as are their calculated structures.

The new carborane derivatives (PhCb°)2X, where PhCb° = 2-Ph-1,2-C2B10H10 and X = S or SO, were prepared from PhCb°Li and SCl2 or SOCl2, respectively. Attempts to prepare cyclic systems (Cb°Y)2, in which two ortho-carboran-di-yl residues Cb° are linked through two bridging units Y (S, SO) are also reported.Figure optionsDownload as PowerPoint slide