Synthesis and structure of rhodium complexes with monoanionic carborane ligand [9-SMe2-7,8-C2B9H10]−

(Rhodacarborane)halide complexes [(η-9-SMe2-7,8-C2B9H10)RhX2]2 (4a: X=Cl; 4b: X=Br; 4c: X=I), which are analogous to [Cp*RhX2]2, were synthesized by reaction of (η-9-SMe2-7,8-C2B9H10)Rh(cod) (cod=1,5-cyclooctadiene) with HX. Compounds 4 were used to prepare several sandwich and half-sandwich complexes containing (η-9-SMe2-7,8-C2B9H10)Rh fragment. 2e-Ligands destroy the dimeric structure of 4 to give the adducts (η-9-SMe2-7,8-C2B9H10)RhLX2, exemplified by preparation of (η-9-SMe2-7,8-C2B9H10)Rh(CO)I2 and (η-9-SMe2-7,8-C2B9H10)Rh(PPh3)Cl2. The reaction of 4a with dppe in the presence of TlBF4 affords the cationic complex [(η-9-SMe2-7,8-C2B9H10)Rh(dppe)Cl]BF4 (7BF4). Sandwich complexes [(η-9-SMe2-7,8-C2B9H10)Rh(η-C5R5)]CF3SO3 (11aCF3SO3: R=H; 11bCF3SO3: R=Me) were obtained by abstracting chloride from 4a by CF3SO3Ag with subsequent treatment with C5R5H. Complex 11bPF6 was prepared by reaction of [Cp*RhCl2]2 with Na[9-SMe2-7,8-C2B9H10]. Complex (η-9-SMe2-7,8-C2B9H10)Rh(η-7,8-C2B9H11), containing two carborane ligands, was obtained by reaction of 4a with Tl[Tl(η-7,8-C2B9H11)]. Structures of 7BF4 and 11bPF6 were confirmed by X-ray diffraction study.