Jump to main content
Jump to site search

Issue 20, 2015
Previous Article Next Article

Hydrothermal synthesis of Group 13 metal trifluoride complexes with neutral N-donor ligands

Author affiliations

Abstract

The reactions of the hydrated Group 13 fluorides, MF3·3H2O (M = Al, Ga or In) with 2,2′:6′,2′′-terpyridyl, 2,2′-bipyridyl or 1,10-phenanthroline under hydrothermal conditions (180 °C/15 h) produced high yields of the complexes [MF3(terpy)]·3H2O, [MF3(bipy)(OH2)]·2H2O and [MF3(phen)(OH2)]. X-Ray crystal structures of [M′F3(terpy)]·3H2O (M′ = Al or Ga), [M′F3(bipy)(OH2)]·2H2O and [GaF3(phen)(OH2)] show that all of them contain distorted octahedral geometries at the metal with mer-trifluoride coordination. Extensive H-bonding (F⋯H–OH) links the molecules. The complexes have been further characterised by microanalysis, IR, 1H, 19F{1H} and 27Al NMR spectroscopy. In contrast, reactions of the trifluorides with the acyclic triamine, N,N,N′,N′,N′′-pentamethyldiethylenetriamine, under similar hydrothermal conditions results in cleavage of the triamine and ring-closure to form the 1,1,4-trimethylpiperazinium cation, [⊂Me2N(CH2)2NMe(CH2)2]+, with fluorometallate anions, and confirmed by X-ray analysis of [⊂Me2N(CH2)2NMe(CH2)2]2[Al2F8(OH2)2]·2H2O. The strongly H-bonded [GaF3(terpy)]·3H2O was also obtained by Cl/F exchange from [GaCl3(terpy)] and [NBu4]F or [K(2,2,2-crypt)]F. Crystallisation of a mixture of [NH4][PF6] and [GaF3(terpy)]·3H2O from aqueous solution produced the edge-bridged cationic complex, [{Ga(terpy)F}2(μ-F)2][PF6]2. The synthesis of the more sterically bulky [GaCl3(tBu3-terpy)] (tBu3-terpy = 4,4′4′′-tris-tBu-2,2′:6′,2′′-terpyridyl) and the crystal structure of [GaCl2(tBu3-terpy)][GaCl4], which contains a trigonal bipyramidal cation, are also reported.

Graphical abstract: Hydrothermal synthesis of Group 13 metal trifluoride complexes with neutral N-donor ligands

Back to tab navigation

Supplementary files

Publication details

The article was received on 20 Mar 2015, accepted on 20 Apr 2015 and first published on 20 Apr 2015


Article type: Paper
DOI: 10.1039/C5DT01120E
Citation: Dalton Trans., 2015,44, 9569-9580
  • Open access: Creative Commons BY license
  •   Request permissions

    Hydrothermal synthesis of Group 13 metal trifluoride complexes with neutral N-donor ligands

    R. Bhalla, W. Levason, S. K. Luthra, G. McRobbie, F. M. Monzittu, J. Palmer, G. Reid, G. Sanderson and W. Zhang, Dalton Trans., 2015, 44, 9569
    DOI: 10.1039/C5DT01120E

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements