The cationic zinc complex [L¹Zn][Al(OC(CF₃)₃)₄] (1) (L¹ = {[(2,4,6‐Me₃–C₆H₂)NC(Me)]₂CH}) bearing a weakly coordinating aluminate anion was obtained from reaction of L¹ZnCl with Li[Al(OC(CF₃)₃)₄]. In addition, base‐stabilized zinc cations [L^1/2Zn(base)₂][X] (2–5) (L² = {[(2,6‐iPr₂–C₆H₃)NC(Me)]₂CH}; X = [Al(OC(CF₃)₃)₄], [B(C₆F₅)₄]) containing weakly coordinating anions and different Lewis bases (dimethylaminopyridine (dmap), tert‐butylpyridine (tBuPy)) were synthesized and structurally characterized. Moreover, the solid‐state structures of L¹ZnMe (6) and the neutral base‐stabilized complexes tBuPy‐Zn(Cl)L¹ (7) and base‐Zn(Me)L² (base = dmap 8, tBuPy 9) are reported and compared with those of 2–5. Preliminary studies showed that 1 is catalytically activity in lactide polymerization at 160 °C.

Dedicated to Prof. H. Nöth on the occasion of his 85th birthday.