Oligonary Nitrides and Oxonitrides of Si, P, Al, and B in Combination with Rare Earth or Transition Metals as well as Molecular Precursor Compounds with Nitrido Bridges M‐N‐Si (M = Ti, Zr, Hf, W, Sn)

Abstract

A novel synthetic approach is presented leading to hitherto unknown nitridosilicates, oxonitridosilicates, oxonitridoaluminosilicates, carbidonitridosilicates, as well as nitridoborates and oxonitridoborates of rare earth elements, alkali, and alkaline earth metals. Typically, the respective metals were reacted with silicon diimide, aluminum nitride, or poly(boron amide imide), respectively, under pure nitrogen atmosphere utilizing a radiofrequency furnace. Usually, the compounds are obtained within short reaction periods as coarsely crystalline products. Zink nitridophosphates of the sodalite structure type were obtained by the reaction of phosphorus nitride imide with zinc or zinc chalcogenides, respectively. Several molecular metal silylamides and imides containing nitridobridges between the metals and silicon were obtained by the reaction of differently chlorinated disilazanes with metal chlorides. During these investigations hitherto unknown bis(trimethylsilyl)ammonium salts have been discovered. Furthermore, we report about the synthesis of N‐silyl metal hydrazides.

Precursor Approach to Lanthanide Dioxo Monocarbodiimides Ln2O2CN2 (Ln=Y, Ho, Er, Yb) by Insertion of CO2 into Organometallic Ln–N Compounds

“…Characterization and thermal degradation of the latter yielding nanocrystalline LnN solids has recently been reported. [10,11] Partial substitution of O by N in lanthanide-containing Si/ N materials (nitridosilicates) [12][13][14] allowed tailor-made tuning of luminescent properties for industrial application of these Abstract: We present two organometallic precursor approaches leading to the hitherto-unknown dioxo monocarbodiimides (Ln 2 O 2 CN 2 ) of the late lanthanides Ho, Er, and Yb as well as yttrium. One involves insertion of CO 2 , and the other one is a straightforward route using a molecular single-source precursor.…”

Synthesis of Rare Earth (Oxo)nitridocarbonates by Employment of Supercritical Carbon Dioxide, Single‐source Precursor, Solid‐State, and Ion Exchange Reactions

“…There are, however, only a few successful synthetic approaches known for the synthesis of such simple compounds with defined composition. Our general interest to target new nitride containing materials with molecular-precursor syntheses, [27,28] led us to utilize organolanthanide molecular precursors for solid-state synthesis of highly activated rare earth nitrido compounds (Scheme 1). On this background molecular precursor compounds with ligands exhibiting an adequate thermal lability for subsequent pyrolysis reactions were targeted.…”

Carbon Dioxide Fixation by Organolanthanides and Thermal Degradation into Amorphous and Higher Condensed Ln/O/C/N Solids

“…Research previously carried out in our laboratory revealed that the introduction of oxygen into Ln nitridosilicates results in interesting luminescent properties. [13][14][15][16][17] The CO 2 reactivity studies of these precursor compounds reported herein enlarge the potential of amorphous O/C/N-containing solids as future reagents for materials science.…”