The organoelement subhalides R 2 Ga 2 I 2 (1) and [R 2 In 2 Cl 2 ] 2 (2) [R = C(SiMe 3 ) 3 ] react with silver acetylacetonate Ag(acac) (acac = [OC(CH 3 )] 2 CH) and lithium acetylacetonate Li(acac), respectively, to yield the di(acetylacetonato)dielement compounds R 2 E 2 (acac) 2 (3: E = Ga; 4: E = In). Both products possess E-E single bonds with relatively long E-E distances of 251.1 (Ga-Ga) and 278.0 pm (In-In). The gallium or indium atoms are terminally coordinated by an alkyl and a bidentate
Treatment of the dimeric indium(II) subhalide (In 2 R 2 Cl 2 ) 2 [R ϭ C(SiMe 3 ) 3 ] possessing In-In single bonds with the dipotassium tetrasilane dianion [K(18-crown-6) ϩ ] 2 [Si(SiMe 3 ) 2 -SiMe 2 -SiMe 2 -Si(SiMe 3 ) 2 ] (1) did not yield the corresponding sixmembered In 2 Si 4 heterocycle by salt elimination. Instead cleavage of the In-In bond occurred, and a compound containing a fivemembered InSi 4 heterocycle (2) was isolated in a low yield. An ionic compound was formed with the indium atoms of the anions Einleitung Elementorganische Subhalogenide des Elements Indium sind leicht durch vorsichtige Oxidation der entsprechenden Indium(I)-Clusterverbindung In 4 [C(SiMe 3 ) 3 ] 4 [1] mit Halogenen oder organischen Halogendonoren zugänglich. Drei unterschiedliche Strukturtypen ließen sich dabei bisher unterscheiden. Der Transfer eines Brommoleküls auf den Cluster führte zur Bildung der Verbindung In 4 Br 2 [C(SiMe 3 ) 3 ] 4 , in der die tetraedrische Anordnung der Indiumatome erhalten blieb und eine Fläche sowie eine Kante des Tetraeders durch jeweils ein Bromatom überbrückt wurden [2]. Elementares Iod unter dem polarisierenden Einfluss des entsprechenden Aluminiumtrihalogenids ergab die Verbindung In 3 I 2 [C(SiMe 3 ) 3 ] 3 mit einer Kette aus drei Indiumatomen, die durch In-In-Einfachbindungen miteinander verbunden sind [3]. Während in beiden Fällen an den Indiumatomen gebrochene mittlere Oxidationsstufen von ϩ1,5 bzw. ϩ1,66 auftraten, führte die vollständige Oxidation aller vier beteiligten Indiumatome nach ϩII zu den Subhalogeniden {In 2 X 2 [C(SiMe 3 ) 3 ] 2 } 2 (X ϭ Cl, Br), in denen zwei In-In-Bindungen durch vier Halogenatome zu einer Realgar-artigen Struktur miteinander verbrückt wurden 2321 coordinated by two silicon and two chlorine atoms. The counterion [K 2 (18-crown-6) 3 ] 2ϩ contained two potassium atoms bridged by a crown ether molecule. Compound 2 and the corresponding gallium derivative 3 were obtained on a specific route by the reaction of the tetrasilane dianion with indium or gallium trichloride.
Terminal and Bridging Coordination of Indium‐Indium Bonds – Remarkable Polymorphism with the Compound In2R2[(OCC6H5)2CH]2 [R = C(SiMe3)3]
Treatment of the dimeric indium(II) subhalide (In2R2Cl2)2 (1) [R = C(SiMe3)3] with four equivalents of lithium dipivaloylmethanide or lithium dibenzoylmethanide afforded by the release of lithium chloride the corresponding diindium diacetylacetonates (2 and 3). The In‐In single bonds of the products were terminally coordinated by chelating acectylacetonato ligands and the bulky alkyl groups. Three different crystal structures were determined for the dibenzoylmethanide derivative 3 which in the solid state adopted trans and gauche conformations across the In‐In bonds. In contrast to the terminally arranged acetylacetonato ligands of compounds 2 and 3 alkylbenzoato ligands R‐COO− (3,5‐dimethylbenzoate and p‐tert‐butylbenzoate) gave the bridging coordination of the In‐In bonds by two chelating carboxylato groups (4 and 5). This particular coordination caused a strong shortening of the In‐In bond length in 4 compared to the unsupported bonds in 2 and 3 (264.6 versus 274.7 to 279.3 pm).
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