Terminale und verbrückende Koordination von Indium‐Indium‐Bindungen – bemerkenswerte Polymorphie an der Verbindung In2R2[(OCC6H5)2CH]2 [R = C(SiMe3)3

Abstract

AbstractTerminal 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).