The reaction of LZnH (1) {L = Mesnacnac = [(2,4,6‐Me₃C₆H₂)NC(Me)]₂CH} with 4‐(dimethylamino)pyridine (dmap) yielded the Lewis acid–base adduct LZn(H)dmap (2), whereas LZn(Cl)dmap (3) was obtained from the equimolar reaction of LZnCl with dmap. In addition, reactions of 1 with di‐tert‐butylcarbodiimide [C(NtBu)₂] and tert‐butyl thioisocyanate (tBuNCS) proceeded with insertion of the heterocumulene into the Zn–H bond and formation of [LZn(tBuNC(H)NtBu)] (4) and [LZn(tBuNC(H)S)] (5), whereas 1 reacted with Me₃SiN₃ with the elimination of Me₃SiH and formation of [LZnN₃]₂ (6). Moreover, the reaction of 1 with cyclohexene oxide (CHO) occurred with ring opening and formation of [LZnOCy]₂ (7) (Cy = cyclohexyl). Complexes 2–7 were characterized by multinuclear NMR (¹H, ¹³C) and IR spectroscopy, elemental analyses and by single‐crystal X‐ray diffraction (2, 3, 6, 7).

Dedicated to Prof. Dieter Fenske on the occasion of his 70th birthday.