Mixed‐Anion Aggregates of Metalated Organics: Preparation and Structure of the Mixed‐Anion Tetramer (PhO^⊖Li^⊕ · HMPA)₃(μ₃‐HMPA · Li^⊕)NCS^⊖

Combination of the ammonium salt method and normal metalation makes it possible to construct in a controlled fashion the inorganic/organic lithium complex 1. BuLi, NH₄NCS, phenol, and HMPA (4: 1 : 3 : 4) in toluene afforded the air‐sensitive compound 1 in over 60% yield. Compound 1 contains three terminal HMPA ligands and one terminal NCS ligand as well as three μ₃‐bridging PhO ligands and one μ₃‐bridging HMPA ligand. The analogous complex containing four PhO ligands and no NCS ligand was also synthesized. The latter is completely inert toward water and air. (Figure Presented.)