Hydrothermal synthesis of Group 13 metal trifluoride complexes with neutral N-donor ligandsDedicated to the memory of Professor Ken Wade, FRS, in recognition of his many significant contributions to inorganic chemistry.Electronic supplementary information (ESI) available: X-ray structure of [⊂Me2N(CH2)2NMe(CH2)2]Cl. CCDC 1053047-1053048 and 1053152-1053158. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt01120e

The reactions of the hydrated Group 13 fluorides, MF 3 ·3H 2 O (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 [MF 3 (terpy)]·3H 2 O, [MF 3 (bipy)(OH 2 )]·2H 2 O and [MF 3 (phen)(OH 2 )]. X-Ray crystal structures of [M′F 3 (terpy)]·3H 2 O (M′ = Al or Ga), [M′F 3 (bipy)(OH 2 )]·2H 2 O and [GaF 3 (phen)(OH 2 )] 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, 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, [⊂Me 2 N(CH 2 ) 2 NMe(CH 2 ) 2 ] + , with fluorometallate anions, and confirmed by X-ray analysis of [⊂Me 2 N(CH 2 ) 2 NMe(CH 2 ) 2 ] 2 [Al 2 F 8 (OH 2 ) 2 ]·2H 2 O. The strongly H-bonded [GaF 3 (terpy)]·3H 2 O was also obtained by Cl/F exchange from [GaCl 3 (terpy)] and [NBu 4 ]F or [K(2,2,2-crypt)]F. Crystallisation of a mixture of [NH 4 ][PF 6 ] and [GaF 3 (terpy)]·3H 2 O from aqueous solution produced the edge-bridged cationic complex, [{Ga(terpy)F} 2 (μ-F) 2 ][PF 6 ] 2 . The synthesis of the more sterically bulky [GaCl 3 ( t Bu 3 -terpy)] ( t Bu 3 -terpy = 4,4′4′′-tris- t Bu-2,2′:6′,2′′-terpyridyl) and the crystal structure of [GaCl 2 ( t Bu 3 -terpy)][GaCl 4 ], which contains a trigonal bipyramidal cation, are also reported. MF 3 ·3H 2 O (M = Al, Ga or In) react with neutral imine ligands under hydrothermal conditions to yield mer -trifluoro complexes with extensive H-bonding.