Silylchalcogenolates MESiR^tBu₂ (M = Na, Cu, Zn, Fe; E = S, Se, Te; R = ^tBu, Ph) and Disilyldichalcogenides ^tBu₂RSiE−ESiR^tBu₂ (E = S, Se, Te; R = ^tBu, Ph):  Synthesis, Properties, and Structures

The sodium silyl chalcogenolates NaESiR^tBu₂ (R = Ph, ^tBu; E = S, Se, Te), accessible by the nucleophilic degradation of S, Se, or Te by the sodium silanides NaSiR^tBu₂ (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(SSiPh^tBu₂)]₄ and [ZnCl(SSi^tBu₃)(THF)]₂, have been synthesized by metathesis reactions of CuCl with NaSSiPh^tBu₂ and of ZnCl₂ with NaSSi^tBu₃, respectively. The solid-state structures of the transition metal thiolates have been determined. The compounds ^tBu₂RSiE−ESiR^tBu₂ (R = Ph, ^tBu; E = S, Se, Te) are accessible via air oxidation. With the exception of ^tBu₃SiS−SSi^tBu₃, these compounds were analyzed using X-ray crystallography and represent the first structurally characterized silylated heavy dichalcogenides. Oxidative addition of ^tBu₃SiTe−TeSi^tBu₃ to Fe(CO)₅ yields [Fe(TeSi^tBu₃)(CO)₃]₂, which has also been structurally characterized.