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 (FH-OH) links the molecules. The complexes have been further characterised by microanalysis, IR, (1)H, (19)F{(1)H} and (27)Al 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((t)Bu3-terpy)] ((t)Bu3-terpy = 4,4'4''-tris-(t)Bu-2,2':6',2''-terpyridyl) and the crystal structure of [GaCl2((t)Bu3-terpy)][GaCl4], which contains a trigonal bipyramidal cation, are also reported.
Highlights
The anhydrous Group 13 metal fluorides MF3 (M = Al, Ga or In) are inert polymeric solids and generally unreactive towards neutral ligands
Gallium and indium fluorides with NH3 ligands have been formed from the reaction of AlN or InN with NH4F in supercritical ammonia at 400 °C, from NH4F or NH4HF2 and elemental Ga, and from [NH4]3[MF6] and gaseous NH3, or MF3·3H2O and liquid NH3.5–9 The structures are usually polymeric with F-bridges
The same approach was extended to reactions with N,N,N′,N′,N′′-pentamethyldiethylenetriamine (PMDTA), and to the diimines, 2,2′-bipyridyl and 1,10-phenanthroline
Summary
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)]. Method as for [AlF3(terpy)]·3H2O using InF3·3H2O (0.200 g, 0.89 mmol) and bipy (0.138 g, 0.89 mmol), yielding a pale yellow solid. The reaction of the MF3·3H2O with terpy in a 1 : 1 molar ratio in water at 180 °C/15 h, followed by removal of the solvent in vacuo at room temperature, gave high yields of the [MF3(terpy)]·3H2O as pale orange solids.
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