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Oxidative formation of phosphinyl radicals from a trigonal pyramidal terminal phosphide Rh(i) complex, with an unusually long Rh-P bond.
Journal article

Oxidative formation of phosphinyl radicals from a trigonal pyramidal terminal phosphide Rh(i) complex, with an unusually long Rh-P bond.

  • Fischbach U Cilag AG, 8200 Schaffhausen, Switzerland.
  • Trincado M Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland. trincado@inorg.chem.ethz.ch gruetzmacher@inorg.chem.ethz.ch.
  • Grützmacher H Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland. trincado@inorg.chem.ethz.ch gruetzmacher@inorg.chem.ethz.ch.
  • 2017-02-21
Published in:
  • Dalton transactions (Cambridge, England : 2003). - 2017
Inorganic Chemistry
English A rhodium complex containing a tetrapodal triolefin ligand (trop3P) and a phosphanyl ligand (PPh2-) has been prepared and characterised. The special structural confinements of the tetradentate ligand impose an unusually long Rh-PPh2 bond. Chemical oxidation of the complex with FcOTf affords [Rh(OTf)(trop3P)] and plausibly phosphanyl radicals, which react instantly with a spin trap reagent forming a nitroxide-based persistent radical, undergo HAT with silanes or dimerise to the corresponding diphosphine (PPh2)2. Chemical oxidation with a peroxide leads to complex [Rh(POPh2)(trop3P)] which is photolabile and loses the Ph2PO moiety upon irradiation with UV/Vis light in CH2Cl2.
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  • English
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https://sonar.ch/global/documents/217697
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