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Main group complexes of group 15 and group 16 Ligands.

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
Hill, Nicholas James

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.

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Published date: 2002

Identifiers

Local EPrints ID: 464808
URI: http://eprints.soton.ac.uk/id/eprint/464808
PURE UUID: 81d3cacf-4b9d-43d2-ac9d-a88cd9d6b2f1

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Date deposited: 05 Jul 2022 00:02
Last modified: 05 Jul 2022 03:13

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Author: Nicholas James Hill

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