Zincocene Cp*₂Zn reacts with carbodiimides C(NR)₂ with insertion into the Zn–Cp* bond and formation of [(Cp*C(NR)₂]₂Zn [R = Et (1), iPr (2), Cy (3)]. In addition, the reaction of Cp*₂Zn with CS₂ under dry conditions gives (Cp*CS₂)₂Zn (4), whereas in the presence of a small amount of water [Zn₄(μ₄‐O)(S₂CCp*)₆] (5) is obtained. Compounds 1–4 were characterized by NMR (¹H, ¹³C) and IR spectroscopy as well as elemental analysis and single‐crystal X‐ray diffraction (2–4, 5 of poor quality). The solid‐state structure of 5 is comparable to the carboxylate complex previously obtained from the reaction of Cp*₂Zn with CO₂.

Dedicated to Prof. K. Jurkschat on the Occasion of his 60th Birthday.