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Tellurium(II) and tellurium(IV) complexes of phosphine chalcogenide ligands, synthesis and X-ray structures

Tellurium(II) and tellurium(IV) complexes of phosphine chalcogenide ligands, synthesis and X-ray structures
Tellurium(II) and tellurium(IV) complexes of phosphine chalcogenide ligands, synthesis and X-ray structures
Reaction of TeX4 (X = Cl or Br) with 2 mol. equiv. of OPR3 (R = Me, Et or Ph) gives the distorted octahedral cis-[TeX4(OPR3)2], while the bidentates Ph2P(E)(CH2)nP(E)Ph2 (E = O, n = 1 or 2; E = S, n = 1) give the six-coordinate [TeX4{Ph2P(E)(CH2)nP(E)Ph2}]. These species have been characterised spectroscopically (via 1H and 31P{1H} NMR and IR) and by crystallographic analyses on cis-[TeBr4(OPPh3)2], [TeCl4{Ph2P(O)CH2P(O)Ph2}] and [TeBr4{Ph2P(S)CH2P(S)Ph2}]. The TeX4 (X = Cl or Br) are reduced by Ph2P(S)(CH2)2P(S)Ph2 and Ph2P(Se)CH2P(Se)Ph2, giving the planar, four-coordinate Te(II) species [Te{Ph2P(S)(CH2)2P(S)Ph2}2]2+ (isolated as [(TeCl5)2{?-Ph2P(S)(CH2)2P(S)Ph2}]2? and [TeBr6]2? salts) and [TeBr2{Ph2P(Se)CH2P(Se)Ph2}], all of which have also been identified crystallographically. On the basis of the structural data the Te-based lone pair associated with the Te(IV) species is assumed to occupy the 5s orbital, whereas in the Te(II) complexes the planar coordination is consistent with the two stereochemically active lone pairs occupying the axial sites.
tellurium halide, phosphine oxide, phosphine sulfide, phosphine selenide
0277-5387
4010-4016
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Victor, Majella
b61d9de8-8025-4b28-9c88-b52f7942f0b9
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Victor, Majella
b61d9de8-8025-4b28-9c88-b52f7942f0b9
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Levason, William, Reid, Gillian, Victor, Majella and Zhang, Wenjian (2009) Tellurium(II) and tellurium(IV) complexes of phosphine chalcogenide ligands, synthesis and X-ray structures. Polyhedron, 28 (18), 4010-4016. (doi:10.1016/j.poly.2009.08.025).

Record type: Article

Abstract

Reaction of TeX4 (X = Cl or Br) with 2 mol. equiv. of OPR3 (R = Me, Et or Ph) gives the distorted octahedral cis-[TeX4(OPR3)2], while the bidentates Ph2P(E)(CH2)nP(E)Ph2 (E = O, n = 1 or 2; E = S, n = 1) give the six-coordinate [TeX4{Ph2P(E)(CH2)nP(E)Ph2}]. These species have been characterised spectroscopically (via 1H and 31P{1H} NMR and IR) and by crystallographic analyses on cis-[TeBr4(OPPh3)2], [TeCl4{Ph2P(O)CH2P(O)Ph2}] and [TeBr4{Ph2P(S)CH2P(S)Ph2}]. The TeX4 (X = Cl or Br) are reduced by Ph2P(S)(CH2)2P(S)Ph2 and Ph2P(Se)CH2P(Se)Ph2, giving the planar, four-coordinate Te(II) species [Te{Ph2P(S)(CH2)2P(S)Ph2}2]2+ (isolated as [(TeCl5)2{?-Ph2P(S)(CH2)2P(S)Ph2}]2? and [TeBr6]2? salts) and [TeBr2{Ph2P(Se)CH2P(Se)Ph2}], all of which have also been identified crystallographically. On the basis of the structural data the Te-based lone pair associated with the Te(IV) species is assumed to occupy the 5s orbital, whereas in the Te(II) complexes the planar coordination is consistent with the two stereochemically active lone pairs occupying the axial sites.

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More information

Published date: 8 December 2009
Keywords: tellurium halide, phosphine oxide, phosphine sulfide, phosphine selenide

Identifiers

Local EPrints ID: 146957
URI: http://eprints.soton.ac.uk/id/eprint/146957
ISSN: 0277-5387
PURE UUID: 1c5b1d95-6e1a-4eea-ba56-f15d786e3ea6
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

Catalogue record

Date deposited: 23 Apr 2010 08:20
Last modified: 20 Jul 2019 01:28

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