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Preparation, properties and structures of the first series of organometanic Pt(II) and Pt(IV) complexes with stibine co-ligands

Preparation, properties and structures of the first series of organometanic Pt(II) and Pt(IV) complexes with stibine co-ligands
Preparation, properties and structures of the first series of organometanic Pt(II) and Pt(IV) complexes with stibine co-ligands
The planar Pt(II) monomers [PtMe2(L-L)] and [(PtMe2)(2)(L'-L')(2)] dimers (L-L = R2Sb(CH2)(3)SbR2, o-C6H4(CH2SbMe2)(2); L'-L'= R2SbCH2SbR2; R = Me or Ph) are obtained in good yield via reaction of [PtMe2(SMe2)(2)] with L-L or L'-L' in benzene. The Pt(IV) stibines, [PtMe3(L-L)I] (L-L = R2Sb(CH2)(3)SbR2, o-C6H4(CH2SbMe2)(2) or 2 x SbPh3, SbMePh2 or SbMe2Ph) are obtained by treatment of [PtMe3I] with L-L in chloroform. These represent the first series of stable Pt(IV) stibine complexes. All of the products have been characterised by H-1, C-13{H-1}, Pt-195 NMR spectroscopy, electrospray mass spectrometry and analysis. Crystal structure determinations on [PtMe3{R2Sb(CH2)(3)SbR2}I], [PtMe3 {o-C6H4(CH2SbMe2)(2)}I] and [PtMe3(SbPh3)(2)I] confirm the distorted octahedral environment at Pt, with fac Me groups and mutually cis Sb donor atoms. The Sb-Pt-Sb angle in the seven-membered chelate ring of the o-C6H4(CH2SbMe2)(2) complex is ca. 96 degrees, compared to <90 degrees in the complexes with six-membered chelates. The C-1-distibines R2SbCH2SbR2 afford only the dinuclear [(PtMe3)(2)(mu-R2SbCH2SbR2)(mu-I)(2)] in which the stibine ligand and two I atoms bridge two Pt atoms giving an edge sharing bioctahedral geometry which has been confirmed by a crystal structure analysis. The Pt(II) species undergo oxidative addition with MeI to give the corresponding Pt(IV) species, while the Pt(IV) species reductively eliminate ethane upon thermolysis.
higher oxidation-states, ray crystal-structure, coordination chemistry, bi-dentate, platinum(ii), xylyl
1477-9226
1667-1674
Brown, Michael D.
76a42341-1a1e-4ec9-8cdc-aca9d5e53bf4
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Brown, Michael D.
76a42341-1a1e-4ec9-8cdc-aca9d5e53bf4
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

Brown, Michael D., Levason, William, Reid, Gillian and Webster, Michael (2006) Preparation, properties and structures of the first series of organometanic Pt(II) and Pt(IV) complexes with stibine co-ligands. Dalton Transactions, 1667-1674. (doi:10.1039/b514019f).

Record type: Article

Abstract

The planar Pt(II) monomers [PtMe2(L-L)] and [(PtMe2)(2)(L'-L')(2)] dimers (L-L = R2Sb(CH2)(3)SbR2, o-C6H4(CH2SbMe2)(2); L'-L'= R2SbCH2SbR2; R = Me or Ph) are obtained in good yield via reaction of [PtMe2(SMe2)(2)] with L-L or L'-L' in benzene. The Pt(IV) stibines, [PtMe3(L-L)I] (L-L = R2Sb(CH2)(3)SbR2, o-C6H4(CH2SbMe2)(2) or 2 x SbPh3, SbMePh2 or SbMe2Ph) are obtained by treatment of [PtMe3I] with L-L in chloroform. These represent the first series of stable Pt(IV) stibine complexes. All of the products have been characterised by H-1, C-13{H-1}, Pt-195 NMR spectroscopy, electrospray mass spectrometry and analysis. Crystal structure determinations on [PtMe3{R2Sb(CH2)(3)SbR2}I], [PtMe3 {o-C6H4(CH2SbMe2)(2)}I] and [PtMe3(SbPh3)(2)I] confirm the distorted octahedral environment at Pt, with fac Me groups and mutually cis Sb donor atoms. The Sb-Pt-Sb angle in the seven-membered chelate ring of the o-C6H4(CH2SbMe2)(2) complex is ca. 96 degrees, compared to <90 degrees in the complexes with six-membered chelates. The C-1-distibines R2SbCH2SbR2 afford only the dinuclear [(PtMe3)(2)(mu-R2SbCH2SbR2)(mu-I)(2)] in which the stibine ligand and two I atoms bridge two Pt atoms giving an edge sharing bioctahedral geometry which has been confirmed by a crystal structure analysis. The Pt(II) species undergo oxidative addition with MeI to give the corresponding Pt(IV) species, while the Pt(IV) species reductively eliminate ethane upon thermolysis.

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More information

Published date: 7 April 2006
Keywords: higher oxidation-states, ray crystal-structure, coordination chemistry, bi-dentate, platinum(ii), xylyl
Organisations: Chemistry

Identifiers

Local EPrints ID: 147031
URI: https://eprints.soton.ac.uk/id/eprint/147031
ISSN: 1477-9226
PURE UUID: 02cfdc8e-6e17-4f72-8a11-997ca9f056d9
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: 18 Jun 2010 15:27
Last modified: 14 Jul 2018 00:37

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