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

Synthesis, characterisation and structures of thio-, seleno- and telluro-ether complexes of gallium(III)
Synthesis, characterisation and structures of thio-, seleno- and telluro-ether complexes of gallium(III)
The reactions of GaX3 (X = Cl, Br or I) with SMe2, SeMe2 and TeMe2 (L) in non-coordinating solvents produces only the pseudo-tetrahedral [GaX3L], which have been characterised by IR, Raman and multinuclear NMR (1H, 71Ga, 77Se or 125Te) spectroscopy, and by the crystal structure of [GaCl3(SeMe2)]. The 71Ga NMR resonances show small low frequency shifts for fixed halides as the neutral donors change from S Se Te. Bidentate ligands including MeS(CH2)2SMe, PhS(CH2)2SPh, MeSe(CH2)2SeMe, nBuSe(CH2)2SenBu and MeTe(CH2)3TeMe (L–L) also produce complexes with 4-coordinate gallium centres, [(GaX3)2(-L–L)], confirmed by the crystal structures of [(GaI3)2{-MeS(CH2)2SMe}], [(GaCl3)2{-PhS(CH2)2SPh}] and [(GaCl3)2{-nBuSe(CH2)2SenBu}]. The structural data are consistent with the weaker Lewis acidity of the gallium as the halide co-ligands become heavier. Multinuclear NMR studies suggest that in chlorocarbon solutions partial dissociation of the ligands occur, which increases with the halide co-ligand Cl < Br < I. The o-xylyl dithioether, o-C6H4(CH2SMe)2, despite being pre-organised for chelation, also forms [(GaCl3)2(-L–L)]. The corresponding diselenoether complex decomposes in solution with C–Se bond cleavage to form the selenonium salt [o-C6H4CH2Se(Me)CH2][GaCl4], which was structurally characterised. The ditelluroether o-C6H4(CH2TeMe)2 undergoes rapid C–Te bond fission and rearrangement upon reaction with GaCl3, and the telluronium species [o-C6H4CH2Te(Me)CH2]+ and [MeTe{CH2(o-C6H4)CH2TeMe}2]+ have been identified by ES+ mass spectrometry from their characteristic isotope patterns.
0300-9246
6274
Gurnani, Chitra
18063024-d052-4fe3-8a79-fdecd227bc2c
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
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, Levason, William, Ratnani, Raju, Reid, Gillian and Webster, Michael (2008) Synthesis, characterisation and structures of thio-, seleno- and telluro-ether complexes of gallium(III). Dalton Transactions, 44, 6274. (doi:10.1039/b810005e).

Record type: Article

Abstract

The reactions of GaX3 (X = Cl, Br or I) with SMe2, SeMe2 and TeMe2 (L) in non-coordinating solvents produces only the pseudo-tetrahedral [GaX3L], which have been characterised by IR, Raman and multinuclear NMR (1H, 71Ga, 77Se or 125Te) spectroscopy, and by the crystal structure of [GaCl3(SeMe2)]. The 71Ga NMR resonances show small low frequency shifts for fixed halides as the neutral donors change from S Se Te. Bidentate ligands including MeS(CH2)2SMe, PhS(CH2)2SPh, MeSe(CH2)2SeMe, nBuSe(CH2)2SenBu and MeTe(CH2)3TeMe (L–L) also produce complexes with 4-coordinate gallium centres, [(GaX3)2(-L–L)], confirmed by the crystal structures of [(GaI3)2{-MeS(CH2)2SMe}], [(GaCl3)2{-PhS(CH2)2SPh}] and [(GaCl3)2{-nBuSe(CH2)2SenBu}]. The structural data are consistent with the weaker Lewis acidity of the gallium as the halide co-ligands become heavier. Multinuclear NMR studies suggest that in chlorocarbon solutions partial dissociation of the ligands occur, which increases with the halide co-ligand Cl < Br < I. The o-xylyl dithioether, o-C6H4(CH2SMe)2, despite being pre-organised for chelation, also forms [(GaCl3)2(-L–L)]. The corresponding diselenoether complex decomposes in solution with C–Se bond cleavage to form the selenonium salt [o-C6H4CH2Se(Me)CH2][GaCl4], which was structurally characterised. The ditelluroether o-C6H4(CH2TeMe)2 undergoes rapid C–Te bond fission and rearrangement upon reaction with GaCl3, and the telluronium species [o-C6H4CH2Te(Me)CH2]+ and [MeTe{CH2(o-C6H4)CH2TeMe}2]+ have been identified by ES+ mass spectrometry from their characteristic isotope patterns.

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Published date: 2008

Identifiers

Local EPrints ID: 146983
URI: http://eprints.soton.ac.uk/id/eprint/146983
ISSN: 0300-9246
PURE UUID: 6c5f233d-70b0-4ba3-9b1a-54c285a588ab
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: 23 Apr 2010 08:24
Last modified: 10 Sep 2019 00:57

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Contributors

Author: Chitra Gurnani
Author: William Levason ORCID iD
Author: Raju Ratnani
Author: Gillian Reid ORCID iD
Author: Michael Webster

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