Adducts of organogallium chlorides with hydrazines and the formation of dimeric dialkylgallium hydrazides possessing different ring sizes

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

“…A second principal method involved the treatment of adducts formed by hydrazines and dialkylaluminum or -gallium halides with n-or tert-butyllithium. However, only substitution reactions by the replacement of the chlorine atoms were observed for those compounds bearing small alkyl groups attached to their aluminum or gallium atoms, and successful deprotonation of the hydrazine ligands and the formation of hydrazides were achieved with bulky tert-butyl groups only [6]. Owing to the larger radius of indium atoms all attempts for the generation of indium hydrazides on such a route failed even in the case of adducts derived from di(tert-butyl)indium chloride.…”

“…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.…”

Reactions of Hydrazines with AlH3·NMe2Et – Formation of Aluminum‐Nitrogen Heterocycles

“…The Al···Al vector is bridged by an N 2 Al group, and the N···N vector is bridged by an Al 2 N moiety. The tricyclic structural motif of the molecular core resembles that of the corresponding hydrocarbon tricyclo[4.4.0.0 2,7 ]decane. [29] According to the molecular symmetry in the solid state five different pyrrole rings and three different (ethyl)dimethylamino ligands were observed in the NMR spectra of solutions of 2.…”

“…[2] The reactions of organoaluminum, -gallium or -indium compounds with hydrazine derivatives gave simple adducts in the first step, which could be isolated and characterized in several cases. [3][4][5][6][7][8][9][10] Spontaneous or thermally induced secondary reactions afforded the corresponding hydrazides by salt elimination, the release of alkanes or elemental hydrogen. These compounds were monomeric only in very few cases, [11][12][13] and usually dimeric formula units were obtained containing four-, five-or six-membered heterocycles.…”

“…These compounds were monomeric only in very few cases, [11][12][13] and usually dimeric formula units were obtained containing four-, five-or six-membered heterocycles. [5,7,9,[13][14][15][16][17][18][19][20][21][22][23] Dianionic hydrazinediido ligands form oligomers possessing oligocyclic or cage-like structures. [3,6,10,17,18,[24][25][26] Several effective routes for the synthesis of these hydrazides are known in the literature and comprise the reactions of trialkylelement compounds or dialkylelement hydrides with hydrazines, the salt elimination by treatment of dialkylelement halides with lithium hydrazides and the amide replacement by treatment of aminoalanes with hydrazines.…”