Tungsten Carbonyl σ-Complexes with C-Thioethers Based on 9-Me3N-7,8-C2B9H11

Charge-compensated mono- and bidentate nido-carboranyl thioether ligands [7-MeS-9-Me3N-7,8-C2B9H10], [7-MeS-11-Me3N-7,8-C2B9H10] and [7,8-(MeS)2-9-Me3N-7,8-C2B9H9] were synthesized. They readily react with labile tungsten carbonyl complex W(CO)5(THF) to give the corresponding σ-complexes (CO)5W[7-MeS-9-Me3N-7,8-C2B9H10-κ1-S(7)], (CO)5W[7-MeS-11-Me3N-7,8-C2B9H10-κ1-S(7)] and (CO)5W[nido-7,8-(MeS)2-9-Me3N-7,8-C2B9H9-κ1-S(7)], respectively. The reaction of [7,8-(MeS)2-9-Me3N-7,8-C2B9H9] with W(CO)3(MeCN)3 produced chelate complex (CO)4W[7,8-(MeS)2-9-Me3S-7,8-C2B9H9-κ2-S(7),S(8)]. The synthesized metallocomplexes were characterized by NMR spectroscopy and single crystal X-ray diffraction.