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Phosphine complexes of aluminium(iii) halides – preparation and structural and spectroscopic systematics

Phosphine complexes of aluminium(iii) halides – preparation and structural and spectroscopic systematics
Phosphine complexes of aluminium(iii) halides – preparation and structural and spectroscopic systematics
Six-coordinate pseudo-octahedral complexes trans-[AlX2(L–L)2][AlX4] (X = Cl, Br or I; L–L = o-C6H4(PMe2)2, Me2P(CH2)2PMe2) are produced from reaction of AlX3 with the diphosphine in CH2Cl2 (X = Cl) or toluene (X = Br or I) solution. Four-coordinate dimers [Cl3Al(?-L?–L?)AlCl3] (L?–L? = Me2P(CH2)2PMe2, Cy2P(CH2)2PCy2), and the tetrahedral cation [AlCl2{o-C6H4(PPh2)2}][AlCl4] were also obtained. Both four- and five-coordinate complexes [AlX3(PMe3)] and [AlX3(PMe3)2] could be isolated with PMe3 depending upon the ratio of reagents used. These extremely moisture sensitive complexes have been characterised by microanalysis, IR and multinuclear NMR (1H, 31P{1H} and 27Al) spectroscopy. X-ray crystal structures are reported for [AlCl2{o-C6H4(PMe2)2}2][AlCl4], [AlCl2{Me2P(CH2)2PMe2}2][AlCl4], [Cl3Al{?-Me2P(CH2)2PMe2}AlCl3], [Cl3Al{?-Cy2P(CH2)2PCy2}AlCl3], [AlCl3(PMe3)], [AlCl3(PMe3)2], and for the six-coordinate cation complex [AlCl2{o-C6H4(PPh2)2}2][AlCl4], although a bulk sample of the last could not be isolated. Tertiary arsines (AsPh3 or AsEt3) form only 1 : 1 complexes even with excess arsine present. The unstable [AlCl2{o-C6H4(AsMe2)2}][AlCl4] is also described, and shown to decompose rapidly in CH2Cl2 solution to form the diquaternised diarsine cation [o-C6H4(AsMe2)2(CH2)][AlCl4]2, which was fully characterised. Comparisons are drawn with the corresponding gallium(III) systems (Cheng et al., Inorg. Chem., 2007, 46, 7215–7223) and with AlX3 complexes of Group 16 ligands (George et al., Dalton Trans., 2014, 43, 3637–3648), and it is concluded that the differences between the Al and Ga systems reflect the higher Lewis acidity of aluminium(III) towards soft donor ligands.
0300-9246
14600-14611
Burt, Jennifer
4f8a0b68-2fb3-4136-98ff-70dfe1acba98
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Burt, Jennifer
4f8a0b68-2fb3-4136-98ff-70dfe1acba98
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Burt, Jennifer, Levason, William, Light, Mark E. and Reid, Gillian (2014) Phosphine complexes of aluminium(iii) halides – preparation and structural and spectroscopic systematics. Dalton Transactions, 43 (39), 14600-14611. (doi:10.1039/c4dt02051k).

Record type: Article

Abstract

Six-coordinate pseudo-octahedral complexes trans-[AlX2(L–L)2][AlX4] (X = Cl, Br or I; L–L = o-C6H4(PMe2)2, Me2P(CH2)2PMe2) are produced from reaction of AlX3 with the diphosphine in CH2Cl2 (X = Cl) or toluene (X = Br or I) solution. Four-coordinate dimers [Cl3Al(?-L?–L?)AlCl3] (L?–L? = Me2P(CH2)2PMe2, Cy2P(CH2)2PCy2), and the tetrahedral cation [AlCl2{o-C6H4(PPh2)2}][AlCl4] were also obtained. Both four- and five-coordinate complexes [AlX3(PMe3)] and [AlX3(PMe3)2] could be isolated with PMe3 depending upon the ratio of reagents used. These extremely moisture sensitive complexes have been characterised by microanalysis, IR and multinuclear NMR (1H, 31P{1H} and 27Al) spectroscopy. X-ray crystal structures are reported for [AlCl2{o-C6H4(PMe2)2}2][AlCl4], [AlCl2{Me2P(CH2)2PMe2}2][AlCl4], [Cl3Al{?-Me2P(CH2)2PMe2}AlCl3], [Cl3Al{?-Cy2P(CH2)2PCy2}AlCl3], [AlCl3(PMe3)], [AlCl3(PMe3)2], and for the six-coordinate cation complex [AlCl2{o-C6H4(PPh2)2}2][AlCl4], although a bulk sample of the last could not be isolated. Tertiary arsines (AsPh3 or AsEt3) form only 1 : 1 complexes even with excess arsine present. The unstable [AlCl2{o-C6H4(AsMe2)2}][AlCl4] is also described, and shown to decompose rapidly in CH2Cl2 solution to form the diquaternised diarsine cation [o-C6H4(AsMe2)2(CH2)][AlCl4]2, which was fully characterised. Comparisons are drawn with the corresponding gallium(III) systems (Cheng et al., Inorg. Chem., 2007, 46, 7215–7223) and with AlX3 complexes of Group 16 ligands (George et al., Dalton Trans., 2014, 43, 3637–3648), and it is concluded that the differences between the Al and Ga systems reflect the higher Lewis acidity of aluminium(III) towards soft donor ligands.

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Accepted/In Press date: 8 August 2014
e-pub ahead of print date: 8 August 2014
Published date: 21 October 2014

Identifiers

Local EPrints ID: 385734
URI: http://eprints.soton.ac.uk/id/eprint/385734
ISSN: 0300-9246
PURE UUID: 77226bed-419a-4908-b3a3-028721c0ed10
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 21 Jan 2016 14:43
Last modified: 15 Mar 2024 03:01

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Contributors

Author: Jennifer Burt
Author: William Levason ORCID iD
Author: Mark E. Light ORCID iD
Author: Gillian Reid ORCID iD

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