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

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• 作者：Rajiv Bhalla^a ; Jennifer Burt^b ; Andrew L. Hector^b ; William Levason^b ; ^{wxl@soton.ac.uk" class="auth_mail" title="E-mail the corresponding author} ; Sajinder K. Luthra^c ; Graeme McRobbie^c ; Francesco M. Monzittu^b ; Gillian Reid^b
• 关键词：Aluminium ; Gallium ; Indium ; Fluoride ; Oxygen donor ligands
• 刊名：Polyhedron
• 出版年：2016
• 出版时间：26 February 2016
• 年：2016
• 卷：106
• 期：Complete
• 页码：65-74
• 全文大小：1864 K

文摘

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 κ²-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)].