title: Oxidative formation of phosphinyl radicals from a trigonal pyramidal terminal phosphide Rh(i) complex, with an unusually long Rh-P bond.
abstract: 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-PPh2bond. 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.
authors.affiliation: Cilag AG, 8200 Schaffhausen, Switzerland.
authors.forename: Urs
authors.initials: U
authors.lastname: Fischbach
authors.affiliation: 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.
authors.forename: M
authors.identifier: http://orcid.org/0000-0002-5912-509X
authors.initials: M
authors.lastname: Trincado
authors.affiliation: 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.
authors.forename: Hansjörg
authors.initials: H
authors.lastname: Grützmacher