Deprotonation of the dimethyl sulfide ligand in [Re(bipy)(CO)(3)(SMe2)][OTf] (1) by KN(SiMe3)(2) afforded a mixture of two diastereomers (2M and 2m) in which a C-C bond has been formed between the S-bonded CH2 group and the 2 position of 2,2'-bipyridine. The solid-state structure of the more stable 2,6-Pr-i-BIAN analogue could be determined by X-ray diffraction.