Mixed guanidinato-amido Ge(iv) and Sn(iv) complexes with GeE (E = S, Se) double bond and SnS4, Sn2Se2 rings

Abstract

The first bulky guanidinate supported germathioamide [{ArNC(NⁱPr₂)NAr}GeN(SiMe₃)₂(S)]; (Ar = 2,6-Me₂–C₆H₃) (3) and germaselanoamide [{ArNC(NⁱPr₂)NAr}GeN(SiMe₃)₂(Se)] (4) complexes with GeS (3) and GeSe (4) moieties, have been synthesized and structurally characterized. Both compounds 3 and 4 were prepared by the oxidative addition of elemental sulfur and selenium, respectively, to the heteroleptic germylene complex [{ArNC(NⁱPr₂)NAr}GeN(SiMe₃)₂] (1) in THF/ether at room temperature. Similarly, reaction of compound [{ArNC(NⁱPr₂)NAr}SnN(SiMe₃)₂] (2) with an equimolar amount of elemental chalcogen (S and Se) led to the formation of cyclic tetrasulfido tin [{ArNC(NⁱPr₂)NAr}SnN(SiMe₃)₂(S₄)] (5) with an SnS₄ ring and dimeric bridged seleno tin [{ArNC(NⁱPr₂)NArN(SiMe₃)₂Sn(μ-Se)}₂] (6) with an Sn₂Se₂ ring, respectively. All compounds 3–6 were confirmed by multinuclear NMR spectroscopy, elemental analysis and single crystal X-ray structural analysis.