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Thio-, seleno- and telluro-ether complexes of aluminium(iii) halides: synthesis, structures and properties

Thio-, seleno- and telluro-ether complexes of aluminium(iii) halides: synthesis, structures and properties
Thio-, seleno- and telluro-ether complexes of aluminium(iii) halides: synthesis, structures and properties
The reaction of AlCl3 with Me2E (E = S, Se or Te) or nBu2E (E = Se or Te) in CH2Cl2 under rigorously anhydrous conditions gave the pseudo-tetrahedral complexes [AlCl3(R2E)]. The [AlX3(Me2E)] (X = Br or I, E = S; X = Br, E = Te) were made from toluene solution since attempted syntheses in CH2Cl2 resulted in substantial chloride incorporation. The synthesis of [(AlCl3)2{o-C6H4(CH2SEt)2}], in which the ligand bridges two tetrahedral aluminium centres, and of the six-coordinate trans-[AlX2{MeE(CH2)2EMe}2][AlX4] (X = Cl or Br, E = S, and X = Cl, E = Se) and cis-[AlI2{MeS(CH2)2SMe}2][AlI4] are reported. The tripodal thioether forms [AlCl3{MeC(CH2SMe)3}], which is a chain polymer with ?2-coordinated ligand and a tbp arrangement at Al(III). Chalcogenoether macrocycle complexes [AlCl3([9]aneS3)], [AlCl2([14]aneS4)][AlCl4] and [AlCl2([16]aneSe4)] [AlCl4] are also described. All complexes were characterised by microanalysis, IR and multinuclear NMR (1H, 27Al, 77Se or 125Te) spectroscopy as appropriate. In CH2Cl2 solution [AlCl3(Me2S)] with added Me2S forms [AlCl3(Me2S)2], and the [AlX2{MeS(CH2)2SMe}2][AlX4] exist as mixtures of cis and trans isomers which undergo rapid exchange at ambient temperatures. X-Ray crystal structures are reported for [AlCl3(Me2Se], [AlX3(Me2Te)] (X = Cl or Br), trans-[AlCl2{MeE(CH2)2EMe}2][AlCl4] (E = S or Se), cis-[AlI2{MeS(CH2)2SMe}2][AlI4], [AlCl3{MeC(CH2SMe)3}], and for the sulfonium salt [Me2SH][AlCl4]. The aluminium halide chalcogenoether chemistry is compared with the corresponding gallium and indium systems, and the relative Lewis acidities of the metals discussed. Attempts to use [AlCl3(nBu2E)] (E = Se or Te) as LPCVD reagents to form aluminium chalcogenide films were unsuccessful.
0300-9246
3637-3648
George, Kathryn
1e9bf4f9-226e-446e-9ef3-dd61c7f7aa11
Jura, Marek
d145b3fa-eec4-47d8-b47c-61a2b616bc8f
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
George, Kathryn
1e9bf4f9-226e-446e-9ef3-dd61c7f7aa11
Jura, Marek
d145b3fa-eec4-47d8-b47c-61a2b616bc8f
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

George, Kathryn, Jura, Marek, Levason, William, Light, Mark and Reid, Gillian (2014) Thio-, seleno- and telluro-ether complexes of aluminium(iii) halides: synthesis, structures and properties. Dalton Transactions, 43 (9), 3637-3648. (doi:10.1039/c3dt52991f).

Record type: Article

Abstract

The reaction of AlCl3 with Me2E (E = S, Se or Te) or nBu2E (E = Se or Te) in CH2Cl2 under rigorously anhydrous conditions gave the pseudo-tetrahedral complexes [AlCl3(R2E)]. The [AlX3(Me2E)] (X = Br or I, E = S; X = Br, E = Te) were made from toluene solution since attempted syntheses in CH2Cl2 resulted in substantial chloride incorporation. The synthesis of [(AlCl3)2{o-C6H4(CH2SEt)2}], in which the ligand bridges two tetrahedral aluminium centres, and of the six-coordinate trans-[AlX2{MeE(CH2)2EMe}2][AlX4] (X = Cl or Br, E = S, and X = Cl, E = Se) and cis-[AlI2{MeS(CH2)2SMe}2][AlI4] are reported. The tripodal thioether forms [AlCl3{MeC(CH2SMe)3}], which is a chain polymer with ?2-coordinated ligand and a tbp arrangement at Al(III). Chalcogenoether macrocycle complexes [AlCl3([9]aneS3)], [AlCl2([14]aneS4)][AlCl4] and [AlCl2([16]aneSe4)] [AlCl4] are also described. All complexes were characterised by microanalysis, IR and multinuclear NMR (1H, 27Al, 77Se or 125Te) spectroscopy as appropriate. In CH2Cl2 solution [AlCl3(Me2S)] with added Me2S forms [AlCl3(Me2S)2], and the [AlX2{MeS(CH2)2SMe}2][AlX4] exist as mixtures of cis and trans isomers which undergo rapid exchange at ambient temperatures. X-Ray crystal structures are reported for [AlCl3(Me2Se], [AlX3(Me2Te)] (X = Cl or Br), trans-[AlCl2{MeE(CH2)2EMe}2][AlCl4] (E = S or Se), cis-[AlI2{MeS(CH2)2SMe}2][AlI4], [AlCl3{MeC(CH2SMe)3}], and for the sulfonium salt [Me2SH][AlCl4]. The aluminium halide chalcogenoether chemistry is compared with the corresponding gallium and indium systems, and the relative Lewis acidities of the metals discussed. Attempts to use [AlCl3(nBu2E)] (E = Se or Te) as LPCVD reagents to form aluminium chalcogenide films were unsuccessful.

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e-pub ahead of print date: 7 January 2014
Published date: 7 March 2014
Organisations: Chemistry

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Local EPrints ID: 368642
URI: http://eprints.soton.ac.uk/id/eprint/368642
ISSN: 0300-9246
PURE UUID: 09b23c33-6b67-4493-97ff-bb2800140279
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Mark 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: 06 Sep 2014 12:38
Last modified: 18 Feb 2021 16:52

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Author: Kathryn George
Author: Marek Jura
Author: William Levason ORCID iD
Author: Mark Light ORCID iD
Author: Gillian Reid ORCID iD

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