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Complexes of aluminium, gallium and indium trifluorides with neutral oxygen donor ligands: Synthesis, properties and reactions

Complexes of aluminium, gallium and indium trifluorides with neutral oxygen donor ligands: Synthesis, properties and reactions
Complexes of aluminium, gallium and indium trifluorides with neutral oxygen donor ligands: Synthesis, properties and reactions
The MF3·3H2O (M = Al, Ga or In) dissolve in hot dimethylsulfoxide (dmso) to form [MF3(OH2)2(dmso)]; further dmso is not incorporated even after prolonged reflux. The X-ray structure of [GaF3(OH2)2(dmso)] shows mer fluorides and trans OH2 ligands. The [GaF3(OH2)2(dmso)] reacts with Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) or 2,2?-bipyridyl to give good yields of [GaF3(Me3tacn)]·xH2O and [GaF3(bipy)(OH2)]·2H2O at room temperature, previously obtained from GaF3·3H2O by a hydrothermal route. [MF3(OH2)2(dmso)] (M = Al or Ga) do not react with R3PO (R = Me or Ph) in CH2Cl2 or MeOH, but with pyNO (pyridine-N-oxide), the products were [AlF3(OH2)2(pyNO)] and [GaF3(OH2)2(pyNO)]·pyNO·H2O. The structure of the latter shows equal numbers of the geometric isomers with mer–trans and mer–cis geometries, as well as lattice pyNO and H2O. Pentamethyldiethylenetriamine (PMDTA) and [GaF3(OH2)2(dmso)] react to produce the zwitterion [GaF4(PMDTAH)]·2H2O, which contains ?2-PMDTA with the ‘free’ NMe2 group protonated to balance the charge of the GaF4? unit. Crystals of [?Me2N(CH2)2NMe(CH2)2]2[Ga2F8(OH2)2]·H2O containing a 1,1,4-trimethylpiperazinium cation, were obtained as a minor by-product. The anion is an edge-shared fluoride-bridged dimer, with the coordinated water ligands arranged anti. Attempts to prepare complexes with phosphine or thioether ligands by Cl/F exchange from the corresponding chloro-complexes with [NMe4]F were unsuccessful, halide exchange being accompanied by liberation of the soft donor ligand. X-ray structures are also reported for [Me2NH2][trans-GaF4(OH2)2] and [AlCl3(OAsPh3)]
0277-5387
65-74
Bhalla, Rajiv
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Burt, Jennifer
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Hector, Andrew L.
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Levason, William
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Luthra, Sajinder K.
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McRobbie, Graeme
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Monzittu, Francesco M.
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Reid, Gill
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Bhalla, Rajiv
685dca44-2474-4fca-a7ea-0075d641e7f2
Burt, Jennifer
17920177-82d7-4017-9cc5-1460aff467f9
Hector, Andrew L.
a82fefa2-0ef0-4466-a03d-88e752ad9040
Levason, William
1aee0faa-cd59-4d06-bb7a-9a25a0a561ab
Luthra, Sajinder K.
2ad7947e-6a9e-4472-95b4-87274f4d2f54
McRobbie, Graeme
b12f273f-dd78-4ff8-a423-b0b5158091c7
Monzittu, Francesco M.
0d045a0e-d9b8-451f-bcc6-ccc9474538d2
Reid, Gill
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Bhalla, Rajiv, Burt, Jennifer, Hector, Andrew L., Levason, William, Luthra, Sajinder K., McRobbie, Graeme, Monzittu, Francesco M. and Reid, Gill (2015) Complexes of aluminium, gallium and indium trifluorides with neutral oxygen donor ligands: Synthesis, properties and reactions. Polyhedron, 106, 65-74. (doi:10.1016/j.poly.2015.12.032).

Record type: Article

Abstract

The MF3·3H2O (M = Al, Ga or In) dissolve in hot dimethylsulfoxide (dmso) to form [MF3(OH2)2(dmso)]; further dmso is not incorporated even after prolonged reflux. The X-ray structure of [GaF3(OH2)2(dmso)] shows mer fluorides and trans OH2 ligands. The [GaF3(OH2)2(dmso)] reacts with Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) or 2,2?-bipyridyl to give good yields of [GaF3(Me3tacn)]·xH2O and [GaF3(bipy)(OH2)]·2H2O at room temperature, previously obtained from GaF3·3H2O by a hydrothermal route. [MF3(OH2)2(dmso)] (M = Al or Ga) do not react with R3PO (R = Me or Ph) in CH2Cl2 or MeOH, but with pyNO (pyridine-N-oxide), the products were [AlF3(OH2)2(pyNO)] and [GaF3(OH2)2(pyNO)]·pyNO·H2O. The structure of the latter shows equal numbers of the geometric isomers with mer–trans and mer–cis geometries, as well as lattice pyNO and H2O. Pentamethyldiethylenetriamine (PMDTA) and [GaF3(OH2)2(dmso)] react to produce the zwitterion [GaF4(PMDTAH)]·2H2O, which contains ?2-PMDTA with the ‘free’ NMe2 group protonated to balance the charge of the GaF4? unit. Crystals of [?Me2N(CH2)2NMe(CH2)2]2[Ga2F8(OH2)2]·H2O containing a 1,1,4-trimethylpiperazinium cation, were obtained as a minor by-product. The anion is an edge-shared fluoride-bridged dimer, with the coordinated water ligands arranged anti. Attempts to prepare complexes with phosphine or thioether ligands by Cl/F exchange from the corresponding chloro-complexes with [NMe4]F were unsuccessful, halide exchange being accompanied by liberation of the soft donor ligand. X-ray structures are also reported for [Me2NH2][trans-GaF4(OH2)2] and [AlCl3(OAsPh3)]

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Accepted/In Press date: 11 December 2015
Published date: 19 December 2015
Organisations: Chemistry

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Local EPrints ID: 398637
URI: http://eprints.soton.ac.uk/id/eprint/398637
ISSN: 0277-5387
PURE UUID: ab14df9b-7877-4cfa-88fb-583d0007e24a
ORCID for Gill Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 28 Jul 2016 13:51
Last modified: 17 Dec 2019 02:01

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Contributors

Author: Rajiv Bhalla
Author: Jennifer Burt
Author: Andrew L. Hector
Author: William Levason
Author: Sajinder K. Luthra
Author: Graeme McRobbie
Author: Francesco M. Monzittu
Author: Gill Reid ORCID iD

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