Complexes of aluminium, gallium and indium trifluorides with neutral oxygen donor ligands: Synthesis, properties and reactions

Abstract

The MF3·3H2O (M = Al, Ga or In) dissolve in hot dimethylsulfoxide (dmso) to form [MF3(OH2)2(dmso)]; further dmso is not incorporated even after prolonged reflux. The X-ray structure of [GaF3(OH2)2(dmso)] shows mer fluorides and trans OH2 ligands. The [GaF3(OH2)2(dmso)] reacts with Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) or 2,2?-bipyridyl to give good yields of [GaF3(Me3tacn)]·xH2O and [GaF3(bipy)(OH2)]·2H2O at room temperature, previously obtained from GaF3·3H2O by a hydrothermal route. [MF3(OH2)2(dmso)] (M = Al or Ga) do not react with R3PO (R = Me or Ph) in CH2Cl2 or MeOH, but with pyNO (pyridine-N-oxide), the products were [AlF3(OH2)2(pyNO)] and [GaF3(OH2)2(pyNO)]·pyNO·H2O. The structure of the latter shows equal numbers of the geometric isomers with mer–trans and mer–cis geometries, as well as lattice pyNO and H2O. Pentamethyldiethylenetriamine (PMDTA) and [GaF3(OH2)2(dmso)] react to produce the zwitterion [GaF4(PMDTAH)]·2H2O, which contains ?2-PMDTA with the ‘free’ NMe2 group protonated to balance the charge of the GaF4? unit. Crystals of [?Me2N(CH2)2NMe(CH2)2]2[Ga2F8(OH2)2]·H2O containing a 1,1,4-trimethylpiperazinium cation, were obtained as a minor by-product. The anion is an edge-shared fluoride-bridged dimer, with the coordinated water ligands arranged anti. Attempts to prepare complexes with phosphine or thioether ligands by Cl/F exchange from the corresponding chloro-complexes with [NMe4]F were unsuccessful, halide exchange being accompanied by liberation of the soft donor ligand. X-ray structures are also reported for [Me2NH2][trans-GaF4(OH2)2] and [AlCl3(OAsPh3)]

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ORCID for Gill Reid: orcid.org/0000-0001-5349-3468

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