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

Hydrothermal synthesis of Group 13 metal trifluoride complexes with neutral N-donor ligands
Hydrothermal synthesis of Group 13 metal trifluoride complexes with neutral N-donor ligands
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, 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(?-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.
0300-9246
9569-9580
Bhalla, Rajiv
685dca44-2474-4fca-a7ea-0075d641e7f2
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Luthra, Sajinder K.
2ad7947e-6a9e-4472-95b4-87274f4d2f54
McRobbie, Graeme
b12f273f-dd78-4ff8-a423-b0b5158091c7
Monzittu, Francesco M.
c0124f10-1f2e-47e5-85f4-138fab36b5d4
Palmer, Jazmyn
a4546b8f-d706-403e-96fa-a6cb910635c1
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Sanderson, George
cf0833c6-e2aa-46bf-a216-2f82a53c1269
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Bhalla, Rajiv
685dca44-2474-4fca-a7ea-0075d641e7f2
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Luthra, Sajinder K.
2ad7947e-6a9e-4472-95b4-87274f4d2f54
McRobbie, Graeme
b12f273f-dd78-4ff8-a423-b0b5158091c7
Monzittu, Francesco M.
c0124f10-1f2e-47e5-85f4-138fab36b5d4
Palmer, Jazmyn
a4546b8f-d706-403e-96fa-a6cb910635c1
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Sanderson, George
cf0833c6-e2aa-46bf-a216-2f82a53c1269
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Bhalla, Rajiv, Levason, William, Luthra, Sajinder K., McRobbie, Graeme, Monzittu, Francesco M., Palmer, Jazmyn, Reid, Gillian, Sanderson, George and Zhang, Wenjian (2015) Hydrothermal synthesis of Group 13 metal trifluoride complexes with neutral N-donor ligands. Dalton Transactions, 44 (20), 9569-9580. (doi:10.1039/C5DT01120E). (PMID:25921724)

Record type: Article

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, 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(?-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.

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Accepted/In Press date: 20 April 2015
e-pub ahead of print date: 20 April 2015
Published date: 28 May 2015
Organisations: Chemistry

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Local EPrints ID: 378988
URI: https://eprints.soton.ac.uk/id/eprint/378988
ISSN: 0300-9246
PURE UUID: 3b838929-3025-4ec5-bac7-e0e5a6130e29
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Francesco M. Monzittu: ORCID iD orcid.org/0000-0002-7080-3795
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 13 Jul 2015 09:13
Last modified: 14 Jul 2018 00:37

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