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

摘要

Details are reported of the preparation and X-ray structural characterisation of the new compounds (PhCb degrees)(2)X, where PhCb degrees = 2-Ph-1,2-C2B10H10 and X = S (1) or SO (3), prepared from PhCb degrees Li and SCl2 or SOCl2 respectively, as well as the known compound with X = S-2 (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 S=C dative pi-bonding from their sulfur atoms to the cage hypercarbon atoms and weak exo pi-bonding from the phenyl groups. Attempts to prepare systems (Cb degrees Y)(2), in which two ortho-carboran-di-yl residues Cb degrees are linked through two bridging units Y (S, SO) are also reported, as are their calculated structures. (c) 2005 Elsevier Ltd. All rights reserved.