Synthesis, Isolation and Crystal Structures of the Metalated Ylides [Cy3P-C-SO2Tol]M (M = Li, Na, K).

The preparation and isolation of the metalated ylides [Cy3PCSO2Tol]M ( Cy1-M) (with M = Li, Na, K) are reported. In contrast to its triphenylphosphonium analogue the synthesis of Cy1-M revealed to be less straight forward. Synthetic routes to the phosphonium salt precursor Cy1-H2 via different methods revealed to be unsuccessful or low-yielding. However, nucleophilic attack of the ylide Cy3P = CH2 at toluenesulfonyl fluoride under basic conditions proved to be a high-yielding method directly leading to the ylide Cy1-H. Metalation to the yldiides was finally achieved with strong bases such as nBuLi, NaNH2, or BnK. In the solid state, the lithium compound forms a tetrameric structure consisting of a (C-S-O-Li)4 macrocycle, which incorporates an additional molecule of lithium iodide. The potassium compound forms a C 4-symmetric structure with a (K4O4)2 octahedral prism as central structural motif. Upon deprotonation the P-C-S linkage undergoes a remarkable contraction typical for metalated ylides.