Silylchalcogenolates MESiR^<i>t</i>Bu₂ (M = Na, Cu, Zn, Fe; E = S, Se, Te; R = ^<i>t</i>Bu, Ph) and Disilyldichalcogenides ^<i>t</i>Bu₂RSiE−ESiR^<i>t</i>Bu₂ (E = S, Se, Te; R = ^<i>t</i>Bu, Ph): Synthesis, Properties, and Structures

The sodium silyl chalcogenolates NaESiRtBu2 (R = Ph, tBu; E = S, Se, Te), accessible by the nucleophilic degradation of S, Se, or Te by the sodium silanides NaSiRtBu2 (R = Ph, tBu), have been characterized by X-ray structure analysis. Protonolysis of the sodium silyl chalcogenolates yields the corresponding chalcogenols. The Cu and Zn chalcogenolates, [Cu(SSiPhtBu2)]4 and [ZnCl(SSitBu3)(THF)]2, have been synthesized by metathesis reactions of CuCl with NaSSiPhtBu2 and of ZnCl2 with NaSSitBu3, respectively. The solid-state structures of the transition metal thiolates have been determined. The compounds tBu2RSiE−ESiRtBu2 (R = Ph, tBu; E = S, Se, Te) are accessible via air oxidation. With the exception of tBu3SiS−SSitBu3, these compounds were analyzed using X-ray crystallography and represent the first structurally characterized silylated heavy dichalcogenides. Oxidative addition of tBu3SiTe−TeSitBu3 to Fe(CO)5 yields [Fe(TeSitBu3)(CO)3]2, which has also been structurally characterized.