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Issue 46, 2007
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Synthesis and characterisation of PCsp3P phosphine and phosphinite platinum(II) complexes. Cyclometallation and simple coordination

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Abstract

New and improved preparative routes to the previously known PCP ligands cis-1,3-bis(di-isopropylphosphinito)cyclohexane and cis-1,3-bis[(di-tert-butylphosphino)methyl]cyclohexane are reported. They react with 1 equivalent of dichloro(1,5-cyclooctadiene)platinum(II) [(COD)PtCl2] to give the cis coordinated complex cis-[PtCl2{cis-1,3-bis(di-isopropylphosphinito)}cyclohexane] and the Csp3-H activated complex trans-[PtCl{cis-1,3-bis(di-tert-butylphosphino)}cyclohexane]. The new PCP ligand cis-1,3-bis(di-tert-butylphosphinito)cyclohexane was synthesised and reacts with [(COD)PtCl2] giving the di-nuclear trans-[PtCl2{cis-1,3-bis(di-tert-butylphosphinito)cyclohexane}]2, which is highly insoluble. All metal complexes were characterised with X-ray crystallography. DFT calculations indicate that the inability of the phosphinite ligands to cyclometallate is due to a kinetic barrier, possibly involving an axial–equatorial conformational change necessary for the C–H activation process.

Graphical abstract: Synthesis and characterisation of PCsp3P phosphine and phosphinite platinum(ii) complexes. Cyclometallation and simple coordination

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Publication details

The article was received on 16 Aug 2007, accepted on 12 Sep 2007 and first published on 28 Sep 2007


Article type: Paper
DOI: 10.1039/B712660C
Citation: Dalton Trans., 2007,0, 5427-5433
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    Synthesis and characterisation of PCsp3P phosphine and phosphinite platinum(II) complexes. Cyclometallation and simple coordination

    D. Olsson, A. Arunachalampillai and O. F. Wendt, Dalton Trans., 2007, 0, 5427
    DOI: 10.1039/B712660C

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