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Updated: Jul 10, 2026
Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)
Published on: November 22, 2016
Synthesis and characterisation of PC(sp3)P phosphine and phosphinite platinum(II) complexes. Cyclometallation and
Daniel Olsson1, Athimoolam Arunachalampillai, Ola F Wendt
1Organic Chemistry, Department of Chemistry, Lund University, PO Box 124, S-221 00 Lund, Sweden.
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 C(sp3)-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.
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