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 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 18 were characterized by heteronuclear NMR (1H and 13C) and IR spectroscopy, and the solid state structures of 15 and 9 were determined by single crystal X-ray diffraction.

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Bayram, M., Bläser, D., Wölper, C., Schulz, S., 2020. Synthesis and X-ray crystal structure of diimidosulfinate transition metal complexes. https://doi.org/10.1021/acs.organomet.5b00407
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