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

Bhalla, Rajiv, Burt, Jennifer, Hector, Andrew L., Levason, William, Luthra, Sajinder K., McRobbie, Graeme, Monzittu, Francesco M. and Reid, Gillian (2016) Complexes of aluminium, gallium and indium trifluorides with neutral oxygen donor ligands: synthesis, properties and reactions. Polyhedron, 106 65-74. doi:10.1016/j.poly.2015.12.032


Author Bhalla, Rajiv
Burt, Jennifer
Hector, Andrew L.
Levason, William
Luthra, Sajinder K.
McRobbie, Graeme
Monzittu, Francesco M.
Reid, Gillian
Title Complexes of aluminium, gallium and indium trifluorides with neutral oxygen donor ligands: synthesis, properties and reactions
Journal name Polyhedron   Check publisher's open access policy
ISSN 0277-5387
1873-3719
Publication date 2016-02-26
Year available 2015
Sub-type Article (original research)
DOI 10.1016/j.poly.2015.12.032
Open Access Status DOI
Volume 106
Start page 65
End page 74
Total pages 10
Place of publication Kidlington, Oxford United Kingdom
Publisher Pergamon Press
Language eng
Formatted 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 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)].
Keyword Aluminium
Gallium
Indium
Fluoride
Oxygen donor ligands
Q-Index Code C1
Q-Index Status Provisional Code
Grant ID EP/1033394/1
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2016 Collection
Centre for Advanced Imaging Publications
 
Versions
Version Filter Type
Citation counts: TR Web of Science Citation Count  Cited 3 times in Thomson Reuters Web of Science Article | Citations
Scopus Citation Count Cited 3 times in Scopus Article | Citations
Google Scholar Search Google Scholar
Created: Tue, 02 Feb 2016, 10:21:39 EST by System User on behalf of Centre for Advanced Imaging