Synthesis and Structure of Mes*AlN(Ph)Al(Mes*)N(Ph)NPh:  A Formal Aluminum−Nitrogen Analog of the Cyclopentadienide Ion

Synthesis of a GaN Cage Compound with a Hydrazinetetraide Fragment, [NN]4−, Stabilised by Six Gallium Atoms

“…Such compounds are conveniently synthesised from 1) trialkylelement compounds or dialkylelement hydrides and hydrazines via the intermediate formation of adducts, 2) dialkylelement halides or their hydrazine adducts upon treatment with lithium hydrazides or butyllithium, 3) aminoalanes and hydrazines, and 4) the reactions of compounds with suitable AlÀ H and C=N functionalities (hydroalumination). [7,10,11] The processes during the thermal decomposition of these hydrazides to form AlN or GaN are poorly understood, and we are currently trying to establish a better understanding of the underlying chemistry by investigating the controlled and, where possible, stepwise thermolysis of well-defined precursors and the isolation and characterisation of the resulting intermediates. Initial progress has revealed that controlled heating of the reagents has led in several cases to cage compounds with interesting structural motifs.…”

Dimethylindium hydrazides [Me2In-NH-NHR]2 (R=CMe3, C6H5)

“…However, more systematic experiments are required to get a concise impression of the principal applicability of these precursors. Secondly, these hydrazides showed a nice coordination behaviour owing to their bidentate character with lone electron pairs at two neighbouring nitrogen atoms [2], and many different structural motifs were detected with the formation of adducts [3][4][5][6], of monomers containing ''side-on'' coordinated hydrazide groups [7][8][9], of dimers possessing heterocycles [5,8,[10][11][12][13][14][15][16], and of oligomeric compounds with a cage-like arrangement of metal and nitrogen atoms [5,13,14,[17][18][19][20]. In the past, most work has been done with respect to the synthesis and structural characterization of dialkylelementhydrazides of the elements aluminum and gallium.…”

Phenylhydrazine Compounds of Aluminum and Gallium – from Adducts to Cyclic Hydrazides and Cages

“…oligozyklische oder käfigartige Verbindungen mit dianionischen Hydrazinliganden treten dagegen seltener auf [3, 6, 10, 17, 18, 28Ϫ31]. Die Hydroaluminierung von geeigneten Distickstoffverbindungen stellt eine effektive Alternative zur Synthese von Hydraziden dar, ihre Anwendung blieb aber bisher auf wenige Beispiele begrenzt [20,31,32].…”