Main group complexes of group 15 and group 16 Ligands.
Main group complexes of group 15 and group 16 Ligands.
Complexes of MX3 (M = As, Sb or Bi; X = C1, Br or I) with the phosphine and arsine ligands oC6H4(ER2)2, EMe3 and MeC(CH2AsMe2)3 (E = P or As, R = Me or Ph) were synthesised and characterised by 1H- and 31P{-H}-NMR and IR spectroscopy, microanalysis and X-ray crystallography. Most of the structurally characterized [MX3{o-C6H4(ER2)2}] complexes adopt a m2halide bridged M2X6 dimer structure, with the bridge comprised of primary and secondary M-X bonds, and the ligand bound cis. The [AsC13(PMe3)] complex forms a weakly associated chain polymer in the solid state, comprised of planar As2C16 dimer units with axial, mutually anti PMe3 ligands.
Complexes of SbX3(X = C1, Br or I) with the chalcogenoethers MeE(CH2)nEMe (E = S or Se, n = 2 or 3) were prepared and characterised by 1H-NMR, IR and microanalysis. X-ray diffraction studies upon a number of examples revealed a diverse array of extended structures. The [SbX3{MeS(CH2)nSMe}] (X = C1, n = 2; X = Br, n = 3) adducts exist as three-dimensional networks and display an unusual mixed bridging/terminal thioether bonding mode. The [SbC13{MeSe(CH2)3SeMe] complex adopts a one-dimensional chain comprised of Sb2C16 dimers linked by bridging MeSe(CH2)3SeMe ligands. Complexes of SbX3 with the thiacrowns [N]aneS4 (X = C1, Br; N = 12, 14 or 16) were characterised as above. All were of 1:1 stoichiometry except for the structurally characterised [(SbBr3)2([14]aneS4}] species which displayed a two-dimensional sheet structure comprised of Sb2Br6 units linked by the macrocycle.
Complexes of AsX3 (X = C1, Br or I) with MeE(CH2)nEMe (E = S or Se, n = 2 or 3, [9]aneS3 [14]aneS4 (X = C1 only), [8]aneSe2 (X = C1, Br), [16]aneSe4 (X = C1, Br) and [24]aneSe6 (X = C1, Br) were synthesised and characterised as above. [AsX3{MeS(CH2)2SMe}] (X = Br, I) exist as discrete dimeric molecules similar to the [MX3{oC6H4(ER2)2}] complexes, while [AsC13([9]aneS3)] consists of an AsC13 unit face-capped by the ligand.
University of Southampton
Hill, Nicholas James
c7d5e880-213a-4491-834e-cdfa4c145300
2002
Hill, Nicholas James
c7d5e880-213a-4491-834e-cdfa4c145300
Hill, Nicholas James
(2002)
Main group complexes of group 15 and group 16 Ligands.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Complexes of MX3 (M = As, Sb or Bi; X = C1, Br or I) with the phosphine and arsine ligands oC6H4(ER2)2, EMe3 and MeC(CH2AsMe2)3 (E = P or As, R = Me or Ph) were synthesised and characterised by 1H- and 31P{-H}-NMR and IR spectroscopy, microanalysis and X-ray crystallography. Most of the structurally characterized [MX3{o-C6H4(ER2)2}] complexes adopt a m2halide bridged M2X6 dimer structure, with the bridge comprised of primary and secondary M-X bonds, and the ligand bound cis. The [AsC13(PMe3)] complex forms a weakly associated chain polymer in the solid state, comprised of planar As2C16 dimer units with axial, mutually anti PMe3 ligands.
Complexes of SbX3(X = C1, Br or I) with the chalcogenoethers MeE(CH2)nEMe (E = S or Se, n = 2 or 3) were prepared and characterised by 1H-NMR, IR and microanalysis. X-ray diffraction studies upon a number of examples revealed a diverse array of extended structures. The [SbX3{MeS(CH2)nSMe}] (X = C1, n = 2; X = Br, n = 3) adducts exist as three-dimensional networks and display an unusual mixed bridging/terminal thioether bonding mode. The [SbC13{MeSe(CH2)3SeMe] complex adopts a one-dimensional chain comprised of Sb2C16 dimers linked by bridging MeSe(CH2)3SeMe ligands. Complexes of SbX3 with the thiacrowns [N]aneS4 (X = C1, Br; N = 12, 14 or 16) were characterised as above. All were of 1:1 stoichiometry except for the structurally characterised [(SbBr3)2([14]aneS4}] species which displayed a two-dimensional sheet structure comprised of Sb2Br6 units linked by the macrocycle.
Complexes of AsX3 (X = C1, Br or I) with MeE(CH2)nEMe (E = S or Se, n = 2 or 3, [9]aneS3 [14]aneS4 (X = C1 only), [8]aneSe2 (X = C1, Br), [16]aneSe4 (X = C1, Br) and [24]aneSe6 (X = C1, Br) were synthesised and characterised as above. [AsX3{MeS(CH2)2SMe}] (X = Br, I) exist as discrete dimeric molecules similar to the [MX3{oC6H4(ER2)2}] complexes, while [AsC13([9]aneS3)] consists of an AsC13 unit face-capped by the ligand.
Text
881492.pdf
- Version of Record
More information
Published date: 2002
Identifiers
Local EPrints ID: 464808
URI: http://eprints.soton.ac.uk/id/eprint/464808
PURE UUID: 81d3cacf-4b9d-43d2-ac9d-a88cd9d6b2f1
Catalogue record
Date deposited: 05 Jul 2022 00:02
Last modified: 16 Mar 2024 19:45
Export record
Contributors
Author:
Nicholas James Hill
Download statistics
Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.
View more statistics