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Synthesis, characterisation and structures of thio-, seleno- and telluro-ether complexes of indium(III) halides

Synthesis, characterisation and structures of thio-, seleno- and telluro-ether complexes of indium(III) halides
Synthesis, characterisation and structures of thio-, seleno- and telluro-ether complexes of indium(III) halides
The indium(III) halo-bridged octahedral dimers [InX2(L–L)(-X)2InX2(L–L)] (X = Cl: L–L = MeS(CH2)2SMe, MeSe(CH2)2SeMe, nBuSe(CH2)2SenBu), the ionic trans-[InX2(L–L)2][InX4] (X = Cl: L–L = iPrS(CH2)2SiPr; X = Br: L–L = MeS(CH2)2SMe, iPrS(CH2)2SiPr, MeSe(CH2)2SeMe), cis-[InCl2(thiamacrocycle)][InCl4] (thiamacrocycle = [12]aneS4 or [14]aneS4) and the neutral, octahedral [InCl3([9]aneS3)] and [InCl3{MeC(CH2SMe)3}] were obtained in good yield by the reaction of 1:1 molar ratios of InX3 with the ligand in anhydrous CH2Cl2 solution. The distorted tetrahedral [InX3(Me2Se)] (X = Cl, Br or I) and [InX3(Me2Te)] (X = Br or I) were obtained from 1:3 and 1:2 molar ratios respectively of InX3 and Me2E (E = Se or Te) also in CH2Cl2. The ligand-bridged, distorted tetrahedral dimers [(InCl3)2{2-o-C6H4(CH2SMe)2}] and [(InCl3)2{2-MeTe(CH2)3TeMe}] are formed even from a 1:1 In:ligand ratio. Key structure types were confirmed from crystal structures of [InCl2{RSe(CH2)2SeR}(-Cl)2InCl2{RSe(CH2)2SeR2}] (R = Me or nBu), trans-[InX2{iPrS(CH2)2SiPr}2][InX4] (X = Cl or Br), trans-[InBr2{MeSe(CH2)2SeMe}2][InBr4], cis-[InCl2([14]aneS4)][InCl4] and [InBr3(Me2Se)]. The bulk complexes have been characterised by IR and Raman spectroscopy and microanalyses, while 1H, 77Se{1H} and 125Te{1H} NMR spectroscopy show that the compounds are extremely labile in solution and undergo rapid dynamic exchange equilibria. Comparisons are drawn between these structurally rather diverse In(III) chalcogenoether complexes and the corresponding Ga(III) species (all of which are neutral and involve distorted tetrahedral coordination). The reaction of TlCl3 with Me2E (E = Se or Te) shows that chlorination of Me2E rather than adduct formation occurs, while no reaction occurred between TlCl3 and Me2S, consistent with Tl(III) being a very poor Lewis acid.
0300-9246
1611-1619
Gurnani, Chitra
18063024-d052-4fe3-8a79-fdecd227bc2c
Jura, Marek
e4a8ae2b-5609-45bb-99d8-a2320b9c89b9
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Ratnani, Raju
0a86c56f-00c6-4c9f-8aa0-52667938ba70
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Gurnani, Chitra
18063024-d052-4fe3-8a79-fdecd227bc2c
Jura, Marek
e4a8ae2b-5609-45bb-99d8-a2320b9c89b9
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Ratnani, Raju
0a86c56f-00c6-4c9f-8aa0-52667938ba70
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

Gurnani, Chitra, Jura, Marek, Levason, William, Ratnani, Raju, Reid, Gillian and Webster, Michael (2009) Synthesis, characterisation and structures of thio-, seleno- and telluro-ether complexes of indium(III) halides. Dalton Transactions, 9, 1611-1619. (doi:10.1039/b816148h).

Record type: Article

Abstract

The indium(III) halo-bridged octahedral dimers [InX2(L–L)(-X)2InX2(L–L)] (X = Cl: L–L = MeS(CH2)2SMe, MeSe(CH2)2SeMe, nBuSe(CH2)2SenBu), the ionic trans-[InX2(L–L)2][InX4] (X = Cl: L–L = iPrS(CH2)2SiPr; X = Br: L–L = MeS(CH2)2SMe, iPrS(CH2)2SiPr, MeSe(CH2)2SeMe), cis-[InCl2(thiamacrocycle)][InCl4] (thiamacrocycle = [12]aneS4 or [14]aneS4) and the neutral, octahedral [InCl3([9]aneS3)] and [InCl3{MeC(CH2SMe)3}] were obtained in good yield by the reaction of 1:1 molar ratios of InX3 with the ligand in anhydrous CH2Cl2 solution. The distorted tetrahedral [InX3(Me2Se)] (X = Cl, Br or I) and [InX3(Me2Te)] (X = Br or I) were obtained from 1:3 and 1:2 molar ratios respectively of InX3 and Me2E (E = Se or Te) also in CH2Cl2. The ligand-bridged, distorted tetrahedral dimers [(InCl3)2{2-o-C6H4(CH2SMe)2}] and [(InCl3)2{2-MeTe(CH2)3TeMe}] are formed even from a 1:1 In:ligand ratio. Key structure types were confirmed from crystal structures of [InCl2{RSe(CH2)2SeR}(-Cl)2InCl2{RSe(CH2)2SeR2}] (R = Me or nBu), trans-[InX2{iPrS(CH2)2SiPr}2][InX4] (X = Cl or Br), trans-[InBr2{MeSe(CH2)2SeMe}2][InBr4], cis-[InCl2([14]aneS4)][InCl4] and [InBr3(Me2Se)]. The bulk complexes have been characterised by IR and Raman spectroscopy and microanalyses, while 1H, 77Se{1H} and 125Te{1H} NMR spectroscopy show that the compounds are extremely labile in solution and undergo rapid dynamic exchange equilibria. Comparisons are drawn between these structurally rather diverse In(III) chalcogenoether complexes and the corresponding Ga(III) species (all of which are neutral and involve distorted tetrahedral coordination). The reaction of TlCl3 with Me2E (E = Se or Te) shows that chlorination of Me2E rather than adduct formation occurs, while no reaction occurred between TlCl3 and Me2S, consistent with Tl(III) being a very poor Lewis acid.

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Published date: 2009

Identifiers

Local EPrints ID: 146951
URI: http://eprints.soton.ac.uk/id/eprint/146951
ISSN: 0300-9246
PURE UUID: 47346e9a-c119-4937-baa7-87cb93ba87d7
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 22 Apr 2010 15:44
Last modified: 17 Sep 2019 01:11

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