Bis(trimethylsilyl)sulfurdiimide S(NSiMe₃)₂ reacts with equimolar amounts of Me₂Zn and Cp*₂Zn either with insertion into the metal–carbon bond and formation of the expected S-methyl diimidosulfinate complex [MeZnN(SiMe₃)S(Me)NSiMe₃]₂1 or the unexpected complex {Me₃SiNS[N(SiMe₃)SNSiMe₃]N(SiMe₃)Zn}₂2. Insertion reactions were also observed with Cp*MMe₃ (M = Ti, Zr, Hf), yielding Cp*(Me)₂M[Me₃SiNS(Me)NSiMe₃] (M = Ti 3, Zr 4, Hf 5), whereas the corresponding Cl-substituted derivatives Cp*(Cl)₂M[(Me₃SiNS(Me)NSiMe₃] (M = Ti 6, Zr 7, Hf 8) were obtained from salt elimination reactions of Li S-methyl diimidosulfinate (Me₃SiN)₂S(Me)Li(thf)]₂9 with Cp*MCl₃. Compounds 1–8 were characterized by heteronuclear NMR (¹H and ¹³C) and IR spectroscopy, and the solid state structures of 1–5 and 9 were determined by single crystal X-ray diffraction.