Über Schwermetallamide. XI. Versuche zur Gewinnung von Titan(IV)‐amid und Darstellung von Kaliumamido‐diimidotitanat(IV)

Abstract

Inhsltsubersieht Es wird die Darstellung von wasserfreiern K,Ti(SCN), beschrieben, das zur Gewinnung yon Ti(NH,), in fliissigem Ammoniak mit KNH, umgeeetzt wurde. Sofern die iiquivalente KNH,-Menge zur Reaktion gebracht wird, enthalten die auefallenden und der Zueernmensetzung des Titan(1V)-imids Ti(NH), nahe kommenden Niederschliige stets SCN-. Werden mehr ah 6Mol KNH, verwendet, so resultieren SCN-freie Niederschliige. Die primiiren Reaktionsprodukte haben die Zusammensetzung K[TiNH(NH,),]. Schon beim Auewaschen mit fliissigem NH, wird KNH, und NH, abgespalton. SummaryThe preparation of anhydrous K,Ti(SCN), is described. It has been used in order t o prepare Ti(NR,), by means of KNH, in liquid ammonia. If, however, the equivalent quantity of KNH, is applied, the rcsulting precipitates of the approximate composition Ti(NH)2 contain SCN-. Increasing the quantity of KNH, up to more than 6 molee per one atom of Ti, the separating solid is free from SCNand has the composition K[TiNH(NH,),], washing this solid with liquid ammonia, KNH, as well as NH, arc split off.

The Complex Amide K2[Zr(NH2)6]

“…In an attempt to reproduce this result, Schmitz‐DuMont only obtained the imide Zr(NH) 2 7. In a targeted synthesis of Ti(NH 2 ) 4 from K 2 [Ti(SCN) 6 ] and KNH 2 in liquid ammonia, only polymerization reactions were observed leading presumably to Ti(NH) 2 and to potassium amido diimido titanate(IV) K[Ti(NH 2 )(NH) 2 ], depending on the stoichiometry of the reaction 7,8. So, the pure amides of group 4 still seem to be elusive.…”

[U(NH3)10]4+ Cations in Azide, Bromide, and Iodide Ammoniates and a Hydrolysis Product with an unprecedented [U(H2O)9]4+ Cation

“…Unfortunately, the products are often amorphous with "ill-defined structures and chemistry". [7][8][9][10][11][12] Recent research also focuses on the ability of U compounds to act as a catalyst for the formation of NH 3 from N 2 and H 2 , [13][14][15] and NH 3 formation has also been shown to occur from uranium nitrido complexes by protonation. [16] Reactions of Th and U compounds with aNH 3 are only poorly explored and especially structural characterization of reaction products is scarce.…”

“…It is clear that decomposition reactions of ammine complexes can afford amides, imides, nitrides or mixed anionic compounds in analogy to olation and oxolation. Unfortunately, the products are often amorphous with “ill‐defined structures and chemistry” [7–12] …”