Organoarsan-stabilisierte und -substituierte Chlorostannylene und -germylene / Chlorostannylenes and Chlorogermylenes Stabilised and Substituted by Organoarsanes

Abstract

<jats:title>Abstract</jats:title><jats:p> Arsinogermylenes, Arsinostannylenes Tin dichloride and the germanium dichloride dioxane complexes react with tri-£er£-butyl-+ — arsane to give ylide-type 1:1 complexes &lt;-Bu3As-MCl2 (M = Sn, Ge). With di-ter£-butyl-(trimethylsilyl)arsane substitution reactions lead to the formation of chlorotrimethylsilane and the arsino-substituted chlorostannylenes and -germylenes £-Bu2As-MCl. Physical properties of these compounds indicate the presence of associated structures with bridging arsino groups and terminal M-Cl functions.</jats:p>

Insertion of Cp*GeCl into a Tungsten−Chlorine Bond and Crystal Structures of the Germylenes Cp*GeCl, [Cp*GeBr]2, and [Cp*Ge][BF4] (Cp* = Pentamethylcyclopentadienyl)

“…The Ge−Cl bond of 2 is with 2.3841(8) Å remarkably long. Thus, this bond is longer than that found for 2 in the gas-phase [Ge−Cl = 2.26(1) Å] and also longer than the Ge−Cl bonds of other germanium(II) chlorides, such as GeCl 2 (g) [Ge−Cl = 2.186(4) Å], GeCl 2 (1,4-dioxane) (average Ge−Cl = 2.265 Å),2b [(C 6 H 3 -2,6-Mes 2 )GeCl] 2 [Ge−Cl = 2.120(2) Å],4i RbGeCl 3 [average Ge−Cl = 2.313(4) Å], [NMe 4 ][GeCl 3 ] [average Ge−Cl = 2.294(7) Å], and [HPMe 3 ][GeCl 3 ] [average Ge−Cl = 2.3071(9) Å] . The Ge−Cl bond of 2 compares well only with that of the germanium(II) compounds (C 5 Me 4 CH 2 CH 2 NMe 2 )GeCl [Ge−Cl = 2.369(1) Å] 13 and (C 5 H 4 CH 2 CH 2 NMe 2 )GeCl [Ge−Cl = 2.381(1) Å], for which intramolecular coordination of the amino functionality in the side chain of the cyclopentadienyl ligand to the germanium atom has been shown to weaken drastically the Ge−Cl bond.…”

“…Most of these compounds are not stable under normal conditions aggregating rapidly to form oligomeric or polymeric products. Stabilization of germylenes can be achieved by n-donor or π-donor substituents, which reduce the electrophilicity of the germanium atom donating electrons into its vacant p-orbital, and by bulky substituents to prevent dimerization or oligomerization . Among the groups, which proved to be very useful for the electronic stabilization of germylenes are cyclopentadienyl ligands.…”