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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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type
Contribution to journal
publication status
published
subject
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
id
3164ada2-d8a6-4be0-a9ff-069616326525 (old id 936372)
date added to LUP
2008-01-21 11:42:42
date last changed
2017-10-01 03:35:04
@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},
  year         = {2007},
}