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

The first bulky guanidinate supported germathioamide [{ArNC((NPr2)-Pr-i)NAr}GeN(SiMe3)(2)(S)]; (Ar = 2,6-Me-2-C6H3) (3) and germaselanoamide [{ArNC((NPr2)-Pr-i)NAr}GeN(SiMe3)(2)(Se)] (4) complexes with Ge=S (3) and Ge=Se (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((NPr2)-Pr-i)NAr}GeN(SiMe3)(2)] (1) in THF/ether at room temperature. Similarly, reaction of compound [{ArNC((NPr2)-Pr-i)NAr}SnN(SiMe3)(2)] (2) with an equimolar amount of elemental chalcogen (S and Se) led to the formation of cyclic tetrasulfido tin [{ArNC((NPr2)-Pr-i)NAr}SnN(SiMe3)(2)(S-4)] (5) with an SnS4 ring and dimeric bridged seleno tin [{ArNC((NPr2)-Pr-i)NArN(SiMe3)(2)Sn(mu-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.