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

Abstract

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.

Reactivity of a Monomeric Aluminium Hydrazide towards Isocyanates and Isothiocyanates: Active Lewis Pair Behaviour versus Classical Insertion Reactions

“…Cleavage of the longer bond should result in the formation of an active Lewis pair, which might be important for an application of 4 in secondary reactions. The N–N bond length [148.0(1) pm] is in the typical range of those of hydrazines …”

“…Monomeric or dimeric compounds having intra‐ or intermolecular bonding interactions between the opposite functionalities have been applied successfully in activation or complexation reactions, although cleavage of the bonds between the Lewis acidic and basic centres is required as an energy‐consuming first step. Aluminium hydrazides are promising candidates for such studies, but they usually form stable dimers with four‐, five‐ or six‐membered Al–N heterocycles . Monomeric aluminium hydrazides are extremely rare , .…”

Anorganische Chemie 2010

“…Die Thermolyse des bicyclischen Galliumhydrazids [(GaMe2)4(NH‐NMe)(NH‐NHMe)2] führt zum Käfig [(GaMe)4(GaMe2)4 (N2)(NH‐NMe)4] (14). Dieser enthält als zentrales Strukturmotiv ein durch sechs Galliumatome stabilisiertes [N‐N]4—‐Hydrazintetraid‐Fragment 1_16…”

Boron, aluminium, gallium, indium and thallium

“…Analysis of the molecular structure reveals the hydrazinetetraide moiety to be the central structural motif, which is stabilised by coordination to six gallium atoms. 268 Cage-shaped gallium complexes with a back-shielding framework of tris-(m-oxybenzyl)arene have been synthesised, the 'bottom' arene rings tuned to modify the characteristic Lewis acidity of the gallium centre. Theoretical calculation as well as catalytic application in a hetero Diels-Alder reaction have been conducted in order to understand the origin of the observed effects.…”