Abstract
Dilithio sulfonyl methandiides are a synthetically and structurally highly interesting group of functionalized geminal dianions. Although very desirable, knowledge of the structure of dilithio methandiides in solution was lacking up to now. Herein, we describe the isolation and determination of the structure of tetrameric dilithio (trimethylsilyl)(phenylsulfonyl) methandiide in solution and in the crystal. The elucidation of the structure of the tetramer is based on crystal structure analysis and (13)C/(6)Li NMR spectroscopic data. A characteristic feature of the structure of the tetramer is the C (2) symmetric C-Li chain, composed of four doubly Li-coordinated dianionic carbon and five Li atoms. Three Li atoms are devoid of a contact to a dianionic C atom. The tetramer, the dianionic C atoms of which undergo fast exchange, is in THF solution in fast equilibrium with a further aggregate, which is stable only at low temperatures.