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

Olsson, Daniel LU ; Arunachalampillai, Athimoolam and Wendt, Ola LU (2007) In Dalton Transactions p.5427-5433
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... (More)
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. (Less)
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publication status
published
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in
Dalton Transactions
pages
5427 - 5433
publisher
Royal Society of Chemistry
external identifiers
  • wos:000251120300010
  • scopus:36248983110
ISSN
1477-9234
DOI
10.1039/b712660c
language
English
LU publication?
yes
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The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240)
id
3164ada2-d8a6-4be0-a9ff-069616326525 (old id 936372)
date added to LUP
2016-04-01 11:34:21
date last changed
2025-04-04 14:03:07
@article{3164ada2-d8a6-4be0-a9ff-069616326525,
  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.}},
  author       = {{Olsson, Daniel and Arunachalampillai, Athimoolam and Wendt, Ola}},
  issn         = {{1477-9234}},
  language     = {{eng}},
  pages        = {{5427--5433}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Dalton Transactions}},
  title        = {{Synthesis and characterisation of PCsp3P phosphine and phosphinite platinum (II) complexes. Cyclometallation and simple coordination}},
  url          = {{http://dx.doi.org/10.1039/b712660c}},
  doi          = {{10.1039/b712660c}},
  year         = {{2007}},
}