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Issue 20, 2015
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Hydrothermal synthesis of Group 13 metal trifluoride complexes with neutral N-donor ligands

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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

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Supplementary files

Article information


Submitted
20 Mar 2015
Accepted
20 Apr 2015
First published
20 Apr 2015

This article is Open Access

Dalton Trans., 2015,44, 9569-9580
Article type
Paper

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

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