Gallium–Gallium Bonds Bridged by Functionalized Carboxylato Ligands 

Abstract

Treatment of the tetraalkyldigallium compound R2Ga–GaR2 [R = CH(SiMe3)2] (1) with a large number of different functionalized carboxylic acids afforded dicarboxylatodigallium compounds R2Ga2(μ‐O2C–R)2, in which two carboxylato ligands bridge the Ga–Ga bonds. The chelating ligands have additional nitrogen, oxygen or phosphorus donor atoms and may be suitable to act as Lewis‐bases to yield supramolecular aggregates in future investigations. Four compounds have been characterized by crystal structure determinations. One gave unprecedented dimeric formula units in the solid state by Ga–N interactions. The similar reaction with isonicotinic acid resulted in the cleavage of the Ga–Ga bond. A tetragallium compound was formed in which four isolated metal atoms were bridged by four organic ligands to give a square molecular core.

p-Block metal complexes with bis(pyrazol-1-yl)acetato ligands

“…29 However, to test the properties, especially in terms of solubility, in vivo stability and bio-distribution, complexes with the stable gallium isotopes 69 Ga/ 71 Ga are usually prepared first. 30 So far, only one gallium complex bearing a μ-O,O-coordinated bdmpza moiety was reported by Uhl et al 18…”

“…Surprisingly, this gallium chemistry is also rarely described, although homoleptic complexes [Ga(Tp) 2 ] + and [Ga(Tp*) 2 ] + have been known since 1988. 15–17 Only one dimeric gallium bpza complex is reported by Uhl et al 18 and was obtained by mixing the gallium precursor [((Me 3 Si) 2 CH) 2 Ga–Ga(CH(SiMe 3 ) 2 ) 2 ] with two equivalents of Hbpza. The result of a single crystal X-ray structure determination exhibits two Ga–Ga bonds (Ga–Ga distance: 2.3944(8) Å) with one carboxylate bridging between the two gallium centres.…”

Anorganische Chemie 2010

“…Dieses enthält in seinem Hohlraum ein fest eingekapseltes THF‐Molekül 1_14. Dieses Konzept der Ga‐Ga‐Bindung als Templat lässt sich erfolgreich auf weitere funktionalisierte Carboxylatoliganden übertragen 1_15. Die Thermolyse des bicyclischen Galliumhydrazids [(GaMe2)4(NH‐NMe)(NH‐NHMe)2] führt zum Käfig [(GaMe)4(GaMe2)4 (N2)(NH‐NMe)4] (14).…”

Boron, aluminium, gallium, indium and thallium

“…The central cavity of the cage has been shown by single crystal X-ray diffraction to contain an encapsulated THF molecule which cannot be removed in vacuo and does not show exchange with a large excess of the solvent. 265,266 Donor assisted tetramethylaluminate/gallate exchange reactions in organolanthanide complexes have been investigated by Anwander and co-workers. La(GaMe 4 ) 3 and (C 5 Me 5 )La(GaMe 4 ) 2 are obtained by reacting La(AlMe 4 ) 3 and (C 5 Me 5 )La(AlMe 4 ) 2 , respectively with GaMe 3 OEt 2 .…”