Reaktionen von elementorganischen Verbindungen mit Indiumatomen in den Oxidationsstufen +I und +II

Elementorganic subhalides of Indium, like In3I3(C(SiMe3)3)3 or [In2X2R2]2 (X = Cl, Br) have only been known with the heavier halogens chlorine to iodine. In this thesis the first synthesis of the subfluorine [In2F2R2]2 is published, which were synthesized using In4R4 and silvertetrafluoroborate. Also the analogue iodine compound could be prepared for the first time using In4R4 and 1,2-Diiodoethane, but the final prove for the structure by crystal structure determination is still missing. These subhalides are very good starting materials to prepare new kinds of compounds by substitution of the halogenatoms with chelating ligands. By the reactions with the analogues of acetylacetone like dipivaloylmethane and dibenzoylmethane, used as lithium-compounds, new compounds with indium-indium-bond were applied. The chelating ligands align terminally to the indiumatoms. The product with dibenzoylmethane shows a remarkable polmorphism wih three different crystal structures with trans- and gauche-conformation of the organic ligands. Lithiumderivatives of analogues of benzoic acid form compounds with bridged indium-indium-bonds. In theses cases the indium-indium-bondlength is shortened by the small O-C-O-angle. A reaction of the subhalides with a tetrasilanediid applied the cleavage of the indium-indium-bond and formation of a InSi4-heterocycle. The indiumatom was oxidised from +II to +III and coordinates two silicon atoms and two chlorine atoms. The negative charge was compensated by the counterion [K2(18-crown-6)3]2+. This ion possesses a remarkable structure with two potassium atoms which are bridged by a molecule of the crownether. This compound and also the analogue Gallium-compound could be synthesized directly by using Indium(III)-chloride respectively Gallium(III)-chloride.