Half-Sandwich Nickelacarboranes Derived from [7-(MeO(CH2)(2)S)-7,8-C2B9H11](-)

New carboranyl thioethers 1-MeO(CH2)(n)S-1,2-C2B10H11 (n = 2, 3) were prepared by the alkylation of the trimethylammonium salt of 1-mercapto-ortho-carborane with 1-bromo- 2-methoxyethane and 1-bromo-3-methoxypropane, respectively. Their deboronation with cesium fluoride in ethanol gave the corresponding nido-carboranes Cs[7-MeO(CH2)(n)S-7,8-C2B9H11] (n = 2, 3). The reactions of Cs[7-MeO(CH2)(2)S-7,8-C2B9H11] with various nickel(II) phosphine complexes [(dppe)NiCl2] and [(R'R2P)(2)NiCl2] (R = R' = Ph, Bu; R = Me, R' = Ph; R = Ph, R' = Me, Et) were studied and a series of nickelacarboranes 3,3-dppe-1-MeO(CH2)(2)S-closo-3,1,2-NiC2B9H10 and 3,3- (R'R2P)(2)-1-MeO(CH2)(2)S-closo-3,1,2-NiC2B9H10 (R = R' = Bu; R = Me, R' = Ph; R = Ph, R' = Me, Et) was prepared. The molecular crystal structure of 3,3-dppe-1-MeO(CH2)(2)S-closo-3,1,2-NiC2B9H10 was determined by single-crystal X-ray diffraction.