Synthese und Strukturuntersuchungen von Pentafluorophenylamido- und Trisamidoaminokomplexen von Elementen der Gruppen 13, 14 und 15 mit hypervalenten intra- und intermolekularen Wechselwirkungen

The purposes of this work were synthesis and structural investigation of pentafluorophenylamido- and trisamidoaminocomplexes of the group 13, 14 and 15 elements with intra- and intermolecular hypervalent interactions. Nitrogen- and fluorine-containing sterically demanding ligands are used to the stabilization of unusual intra- and intermolecular geometries. The results of the efforts towards the new group 13, 14 and 15 amidocompounds are documented in 18 crystal structures. Reactions of pentafluorophenyl-substituted amines DFDPA (decafluorodiphenylamine) and PFAP (2-pentafluoroanilinopyridine) with dialkylamides of In, Bi, and Sb were examined. Some of the synthesized products were structurally characterized. An unusual intramolecular rearrangement is observed for DFDPA-and PFAP-dialkylamidocomplexes of Bi and Sb. A possible SNAr-reaction mechanism is suggested for this rearrangement and founded by theoretical structure calculations. A new method of generation of the atrane fragment in the chemistry of the main group elements via metathetical reaction of the trilithium salts of tetraamines Me3-tren (tris-[2-(methylamino)ethyl]amine) and SiMe3-tren (tris-[2-(trimethylsilylamino)ethyl]amine) with trihalogenides of the group 13, 14 and 15 elements was developed. The first azatranes of Bi, Sb and In were synthesized and structurally characterized. Oligomeric indiumazatranes show unusual sets of the In-N-interatomic distances.