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]


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Scheme 7: Synthesis and molecular structure of MeZnN-(SiMe3)S(Me)NSiMe3]2.

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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).

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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]

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Scheme 8: Synthesis and molecular structure of Cp*(Cl)2M[(Me3SiNS(Me)NSiMe3] (M = Ti, Zr, Hf).


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[2] D. Stalke Chem. Commun. 2012, 48, 9559.

[3] D. Kottmair-Maieron, R. Lechler, J. Weidlein, Z. Anorg. Allg. Chem. 1991, 593, 111.

[4] K. Kaleta, M. Ruhmann, O. Theilmann, S. Roy, T. Beweries, P. Arndt, A. Villinger, E. D. Jemmis, A. Schulz, U. Rosenthal Eur. J.Inorg. Chem. 2012, 611.

[5] R. Hasselbring, I. Leichtweis, M. Noltemeyer, H. W. Roesky, H. G. Schmidt, A. Herzog, Z. Anorg. Allg. Chem. 1993, 619, 1543.

[6] H. W Roesky, H. G. Schmidt, M. Noltemeyer, G. M. Sheldrick, Chem. Ber. 1983, 116, 1411.

[7] C. Hubrich, A. Schulz, A. Villinger Z. Anorg. Allg. Chem. 2007, 633, 2362.

[8] M. Bayram, D. Bläser, C. Wölper, S. Schulz Organometallics 2015, 34, 3421.