Oligonuclear gallium nitrogen cage compounds: molecular intermediates on the way from gallium hydrazides to gallium nitride.

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).

Synthesis of a GaN cage compound with a hydrazinetetraide fragment, [N-N]4-, stabilised by six gallium atoms.

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.