Synthesis and X‑ray Crystal Structure of Diimidosulfinate Transition Metal Complexes

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 <i>S</i>-methyl diimidosulfinate complex [MeZnN­(SiMe₃)­S­(Me)­NSiMe₃]₂ <b>1</b> or the unexpected complex {Me₃SiNS­[N­(SiMe₃)­SNSiMe₃]­N­(SiMe₃)­Zn}₂ <b>2</b>. Insertion reactions were also observed with Cp*MMe₃ (M = Ti, Zr, Hf), yielding Cp*­(Me)₂M­[Me₃SiNS­(Me)­NSiMe₃] (M = Ti <b>3</b>, Zr <b>4</b>, Hf <b>5</b>), whereas the corresponding Cl-substituted derivatives Cp*­(Cl)₂M­[(Me₃SiNS­(Me)­NSiMe₃] (M = Ti <b>6</b>, Zr <b>7</b>, Hf <b>8</b>) were obtained from salt elimination reactions of Li <i>S</i>-methyl diimidosulfinate (Me₃SiN)₂S­(Me)­Li­(thf)]₂ <b>9</b> with Cp*MCl₃. Compounds <b>1</b>–<b>8</b> were characterized by heteronuclear NMR (¹H and ¹³C) and IR spectroscopy, and the solid state structures of <b>1</b>–<b>5</b> and <b>9</b> were determined by single crystal X-ray diffraction