Synthesis and structure of sulfurdiimide complexes
Synthesis and structure of sulfurdiimide complexes
Bis(trimethylsilyl)sulfurdiimide S(NSiMe3)2 readily undergoes insertion reactions with a large variety of metal complexes with formation of metal diimidosulfinates[1-4] and also forms Lewis-adduct with TiCl4, SnCl4 and GaCl3.[5-7] We recently demonstrated that S(NSiMe3)2 reacts with homoleptic group 12 (ZnR2) and heteroleptic group 4 metal complexes Cp*MMe3 (M = Ti, Zr, Hf) with insertion into the metal carbon bond. The reaction with ZnMe2 yielded MeZnN-(SiMe3)S(Me)NSiMe3]2, containing an eight-membered N4S2Zn2 ring as central structural motif, while that with Cp*2Zn yielded the unexpected complex {Me3SiNS[N(SiMe3)-SNSiMe3]N(SiMe3)Zn} and decamethyl-1,1´-dihydrofulvalene as byproduct.[8]
Scheme 7: Synthesis and molecular structure of MeZnN-(SiMe3)S(Me)NSiMe3]2.
Scheme 8: Synthesis and molecular structure of {Me3SiNS[N(SiMe3)-SNSiMe3]N(SiMe3)Zn}.
Insertion reactions were also observed with Cp*MMe3 (M = Ti, Zr, Hf) yielding Cp*(Me)2M[Me3SiNS(Me)NSiMe3] (M = Ti, Zr, Hf).
Scheme 9: Reaction pathway leading to Cp*(Me)2M[Me3SiNS(Me)NSiMe3] (M = Ti 8, Zr 9, Hf 10) and crystal structures of 8, 9, 10.
The analogous Cl-substituted complexes Cp*(Cl)2M[(Me3SiNS(Me)NSiMe3] (M = Ti, Zr, Hf) were formed by reaction of S(NSiMe3)2 with an equimolar amount of methyllithium and subsequent treatment with Cp*MCl3.[8]
Scheme 8: Synthesis and molecular structure of Cp*(Cl)2M[(Me3SiNS(Me)NSiMe3] (M = Ti, Zr, Hf).
References
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[8] M. Bayram, D. Bläser, C. Wölper, S. Schulz Organometallics 2015, 34, 3421.