ic048710j_si_012.rtf (112.11 kB)

Silylchalcogenolates MESiRtBu2 (M = Na, Cu, Zn, Fe; E = S, Se, Te; R = tBu, Ph) and Disilyldichalcogenides tBu2RSiE−ESiRtBu2 (E = S, Se, Te; R = tBu, Ph):  Synthesis, Properties, and Structures

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posted on 16.05.2005, 00:00 by Theresa I. Kückmann, Melina Hermsen, Michael Bolte, Matthias Wagner, Hans-Wolfram Lerner
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.