Gallium hydrazides are potentially applicable as facile starting compounds for the generation of GaN by thermolysis. The decomposition pathways are, however, complicated and depend strongly on the substituents attached to the gallium atoms and the hydrazido groups. This paper describes some systematic investigations into the thermolysis of the gallium hydrazine adduct Bu(t)(3)Ga←NH(2)-NHMe (1a) and the dimeric gallium hydrazides [R(2)Ga(N(2)H(2)R')](2) (2b, R = Bu(t), R' = Bu(t); 2c, R = Pr(i), R' = Ph; 2d, R = Me, R' = Bu(t)) which have four- or five-membered heterocycles in their molecular cores. Heating of the adduct 1a to 170 °C gave the heterocyclic compound Bu(t)(2)Ga(μ-NH(2))[μ-N(Me)-N(=CH(2))]GaBu(t)(2) (3) by cleavage of N-N bonds and rearrangement. 3 was further converted at 400 °C into the tetrameric gallium cyanide (Bu(t)(2)GaCN)(4) (4). The thermolysis of the hydrazide (Bu(t)(2)Ga)(2)(NH-NHBu(t))(2) (2b) at temperatures between 270 and 420 °C resulted in cleavage of all N-N bonds and the formation of an octanuclear gallium imide, (Bu(t)GaNH)(8) (6). The trimeric dialkylgallium amide (Bu(t)(2)GaNH(2))(3) (5) was isolated as an intermediate. Thermolysis of the hydrazides (Pr(i)(2)Ga)(2)(NH-NHPh)(NH(2)-NPh) (2c) and (Me(2)Ga)(2)(NH-NHBu(t))(2) (2d) proceeded in contrast with retention of the N-N bonds and afforded a variety of novel gallium hydrazido cage compounds with four gallium atoms and up to four hydrazido groups in a single molecule: (Pr(i)Ga)(4)(NH-NPh)(3)NH (7), (MeGa)(4)(NH-NBu(t))(4) (8), (MeGa)(4)(NH-NBu(t))(3)NBu(t) (9), and (MeGa)(4)(NHNBu(t))(3)NH (10). Partial hydrolysis gave reproducibly the unique octanuclear mixed hydrazido oxo compound (MeGa)(8)(NHNBu(t))(4)O(4) (11).

Thermolysis of the bicyclic gallium hydrazide [(GaMe(2))(4)(NH-NMe)(NH-NHMe)(2)] (1) yielded the unique cage compound [(GaMe)(4)(GaMe(2))(4)(N(2))(NH-NMe)(4)] (2). Compound 2 contains a remarkable hydrazinetetraide moiety, [N-N](4-), as the central structural motif which is stabilised by coordination to six gallium atoms.

The reactions of trialkyl-element compounds (E ϭ Al, Ga) with hydrazines usually proceed by the intermediate formation of the simple adducts R 3 EǟNH 2 -N(H)-RЈ. However, only one adduct (1; R ϭ iPr, E ϭ Ga) could be isolated and characterized in the reactions of ER 3 compounds bearing relatively small substituents with phenylhydrazine. In all other cases fast secondary processes gave directly the corresponding dimeric hydrazides [R 2 EϪN(H)ϪN(H)-C 6 H 5 ] 2 (2 to 4; R ϭ Me, Et; E ϭ Al, Ga) by gas evolution below room temperature. In contrast, decomposition of the adduct 1 required boiling toluene to produce the hydrazide 5. Compounds 3 and 4 possess four-membered E 2 N 2 heterocycles Einleitung Elementorganische Aluminium-, Gallium-oder Indiumhydrazide stellen als leicht zugängliche Ausgangsverbindungen hervorragende Vorläufer für die thermolytische Abscheidung der entsprechenden Metallnitride dar [1]. Darüber hinaus besitzen sie aber beträchtliches wissenschaftliches Interesse, da die Hydrazinliganden ein bemerkenswertes Koordinationsverhalten aufweisen. Sie besitzen freie Elektronenpaare an miteinander verbundenen Stickstoffatomen und sind daher in der Lage, eine große Vielfalt unterschiedlicher Strukturmotive durch terminale bzw. 1,1oder 1,2-verbrückende Koordination von Metallatomen zu realisieren [2]. Die Darstellung solcher Erdmetallhydrazide gelingt auf unterschiedlichen Wegen durch Salz-, Wasserstoff-oder Alkaneliminierung. Der erste Schritt besteht im allgemeinen aus der Bildung von Addukten zwischen den Hydrazinmolekülen und den koordinativ ungesättigten

Organoelement aluminum, gallium, and indium hydrazides, [R(2)ENHN(H)R'](2) (E = Al, Ga, In), are easily available from the corresponding trialkylelement compounds, ER(3), and hydrazines, H(2)NN(H)R', via elimination of the respective hydrocarbons. Their diverse molecular structures are derived from four-, five-, or six-membered element-nitrogen heterocycles. Their stepwise thermolysis under carefully controlled conditions was shown to proceed along one of several different well-defined routes. Cleavage of the N-N bonds afforded aluminum or gallium imides, [REN(H)](n), with up to eight metal atoms in a single molecule, while preservation of the N-N bonds led to interesting cages in which intact N-N bonds of formally dianionic hydrazinediides bridge the metal atoms via their two adjacent donor atoms. Further thermolysis yielded the amorphous element nitrides via the gradual degradation of the hydrazinediide groups. Several intermediates have been isolated and provided insight in the course of these reactions. A particularly interesting compound was one that features a hydrazinetetraide unit, [N-N](4-), that is stabilized by coordination to six gallium atoms.

Room temperature ionic liquids (RTILs), especially pyrrolidinium based RTILs with bis(trifluoromethane‐sulfonyl)imide (TFSI) as counterion, are frequently proposed as promising electrolyte component candidates thanks to their high thermal as well as high oxidation stability. In order to avoid a resource intensive experimental approach, mainly based on trial and error experiments, a computational screening method for pre‐selecting suitable candidate molecules was adopted and three homologous series compounds were synthesized by modifying the cation structure of pyrrolidinium RTILs. The obtained high purity RTILs: methyl‐methylcarboxymethyl pyrrolidinium TFSI (MMMPyrTFSI), methyl‐ethylcarboxymethyl pyrrolidinium TFSI (MEMPyrTFSI) and methylpropylcarboxymethyl pyrrolidinium TFSI (MPMPyrTFSI) revealed excellent thermal stabilities higher than 300 °C. Furthermore, MMMPyrTFSI and MPMPyrTFSI exhibit high oxidation stability up to 5.4 V vs. Li/Li+. No aluminum corrosion of current collector was observed at 5 V vs. Li/Li+. In addition to that, these RTILs display a superior salt (LiTFSI) solubility (3.0–3.5 M), compared to the unmodified RTIL 1‐butyl‐1‐methylpyrrolidinium TFSI (Pyr14TFSI) (1.5–2.0 M) at room temperature. All these properties make novel ester modified RTILs promising and interesting candidates for application in rechargeable lithium batteries.