When an excess of nBuLi was used in the ortho-dilithiation of thiophenol or 2-trimethylsilylthiophenol in the presence of TMEDA (TMEDA = N,N,N',N'-tetramethylethylenediamine), deprotonation of TMEDA occurred and crystals of [Li3{(2-S-C6H4)(CH2MeNCH2CH2NMe2)(TMEDA)}]2 (1) or [Li4{(2-S-3-SiMe3-C6H3)(CH2MeNCH2CH2NMe2)2(TMEDA)}] (2) were obtained. Molecular orbital calculations on gas-phase 1 and 2 at the DFT B3LYP/6-31G(d) level reproduce the experimental structures fairly well. In spite of the short Li...Li distances, total electron density representations do not support the existence of Li...Li interactions.