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 NaESiR^<i>t</i>Bu₂ (R = Ph, ^<i>t</i>Bu; E = S, Se, Te), accessible by the nucleophilic degradation of S, Se, or Te by the sodium silanides NaSiR^<i>t</i>Bu₂ (R = Ph, ^<i>t</i>Bu), have been characterized by X-ray structure analysis. Protonolysis of the sodium silyl chalcogenolates yields the corresponding chalcogenols. The Cu and Zn chalcogenolates, [Cu(SSiPh^<i>t</i>Bu₂)]₄ and [ZnCl(SSi^<i>t</i>Bu₃)(THF)]₂, have been synthesized by metathesis reactions of CuCl with NaSSiPh^<i>t</i>Bu₂ and of ZnCl₂ with NaSSi^<i>t</i>Bu₃, respectively. The solid-state structures of the transition metal thiolates have been determined. The compounds ^<i>t</i>Bu₂RSiE−ESiR^<i>t</i>Bu₂ (R = Ph, ^<i>t</i>Bu; E = S, Se, Te) are accessible via air oxidation. With the exception of ^<i>t</i>Bu₃SiS−SSi^<i>t</i>Bu₃, these compounds were analyzed using X-ray crystallography and represent the first structurally characterized silylated heavy dichalcogenides. Oxidative addition of ^<i>t</i>Bu₃SiTe−TeSi^<i>t</i>Bu₃ to Fe(CO)₅ yields [Fe(TeSi^<i>t</i>Bu₃)(CO)₃]₂, which has also been structurally characterized.