Aluminum and Gallium Hydrazides Derived from N-Aminopyrrole and N-Aminopiperidine

Abstract

The heterocyclic hydrazine derivatives N-aminopyrrole, H2N-NC4H4, and N-aminopiperidine, H2N-NC5H10, reacted with the hydrides H-Al(CMe3)2 or GaH3NMe2Et by the release of elemental hydrogen and the formation of the corresponding aluminum and gallium hydrazides. These products are dimerized in the solid state via Al-N-Al or Ga-N-Ga bridges and possess four-membered E2N2 heterocycles with two exocyclic N-N bonds.

Ten-Membered Cyclodecatetraene Derivatives Including Two Gallium Atoms: Experimental and Theoretical Studies on Synthesis, Structures, and Their Transformations to Nine- and Five-Membered Gallacycles

“…The bond lengths of Ga–Cl and Ga–N are 2.2293(10) and 2.013(3) Å, respectively. These lengths are comparable to those observed in the usual terminal Ga–Cl single bonds (2.22–2.29 Å) and the nitrogen to gallium coordination bonds (2.01–2.08 Å). , The CC and C–C bond lengths within the GaC 4 ring are 1.343(5)–1.349(4) and 1.529(5) Å, respectively, which are within the ranges in those reported for Lewis-base coordinated gallole derivatives (1.34–1.36 and 1.51–1.53 Å, respectively). , …”

Aluminum, Gallium, and Indium Hydrazides and the Generation of Oligonuclear Element-Nitrogen Cages: Molecular Intermediates on the Way to Element Nitrides

“…Other adducts reported in the literature such as (Me 3 C) 2 ClAl←NH 2 N(H)SiMe 3 and MeCl 2 Ga←NH 2 N(H)CMe 3 contain dialkyl- or monoalkylelement halides coordinated by hydrazine ligands. − As a consequence of the relatively large covalent radius of indium, only the corresponding dialkylindium chloride adducts, R 2 InCl←NH 2 N(H)R′, have coordination numbers larger than 4 at the metal atoms. These result in unusual oligomeric or polymeric structures in the solid state with bridging chlorine and hydrazine ligands .…”

“…The products are monoanionic hydrazides, [N(H)N(H)R′] − (eq ), which in solution and the solid state have dimeric structures with bridging metal atoms. − ,,,− Dissociation to the monomeric formula unit required the addition of ether or tetrahydrofuran . Alternative methods for the synthesis of these hydrazides comprise the reaction of dialkylelement halides with lithium hydrazides, ,, the treatment of adducts, R 2 ClE←NH 2 N(H)R′, with butyllithium, ,, the reaction of dialkylelement hydrides with hydrazines, ,− an amine–hydrazide exchange reaction, and the reduction of diazene with a gallium(I) compound . The reactions of trialkylelement derivatives with hydrazines are clearly superior to other methods because the synthesis of the starting organoelement compounds requires additional steps, the reactions are less selective, the products form complexes with lithium, , and, in some cases, inorganic salts are formed as side products.…”

Reactions of Hydrazines with AlH3·NMe2Et – Formation of Aluminum‐Nitrogen 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.…”