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Issue 13, 2006
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Preparation, properties and structures of the first series of organometallic Pt(II) and Pt(IV) complexes with stibine co-ligands

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Abstract

The planar Pt(II) monomers [PtMe2(L–L)] and [(PtMe2)2(L′–L′)2] dimers (L–L = R2Sb(CH2)3SbR2, 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)3SbR2, o-C6H4(CH2SbMe2)2 or 2 × 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 1H, 13C{1H}, 195Pt NMR spectroscopy, electrospray mass spectrometry and analysis. Crystal structure determinations on [PtMe3{R2Sb(CH2)3SbR2}I], [PtMe3{o-C6H4(CH2SbMe2)2}I] and [PtMe3(SbPh3)2I] 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°, compared to <90° in the complexes with six-membered chelates. The C1-distibines R2SbCH2SbR2 afford only the dinuclear [(PtMe3)2(μ-R2SbCH2SbR2)(μ-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.

Graphical abstract: Preparation, properties and structures of the first series of organometallic Pt(ii) and Pt(iv) complexes with stibine co-ligands

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Publication details

The article was received on 04 Oct 2005, accepted on 09 Nov 2005 and first published on 14 Dec 2005


Article type: Paper
DOI: 10.1039/B514019F
Dalton Trans., 2006, 1667-1674

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

    M. D. Brown, W. Levason, G. Reid and M. Webster, Dalton Trans., 2006, 1667
    DOI: 10.1039/B514019F

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