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. 2016 Sep 19;55(39):11999-2002.
doi: 10.1002/anie.201605687. Epub 2016 Aug 25.

From 0 to II in One-Electron Steps: A Series of Ruthenium Complexes Supported by TropPPh2

Xiuxiu Yang  1 , Thomas L Gianetti  2 , Joshua Harbort  3 , Michael D Wörle  1 , Lilin Tan  1   4 , Cheng-Yong Su  4 , Pascal Jurt  1 , Jeffrey R Harmer  5 , Hansjörg Grützmacher  6   7
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From 0 to II in One-Electron Steps: A Series of Ruthenium Complexes Supported by TropPPh2

Xiuxiu Yang et al. Angew Chem Int Ed Engl. .

Abstract

We report the synthesis of a series of ruthenium complexes supported by the phosphine olefin ligand tropPPh2 (trop=5-H-dibenzo-[a,d]cyclohepten-5-yl) in the oxidation states 0, +I, and +II, formed via successive one-electron oxidization steps from Ru(0) (tropPPh2 )2 . The bidentate character of the tropPPh2 ligand and its steric hindrance force the complexes to adopt uncommon geometries, which were investigated by X-ray diffraction analysis. EPR data of the mononuclear Ru(I) complex reveal couplings of the unpaired spin with the ruthenium and two phosphorus nuclei, as well as the olefinic protons which show that the spin is mainly localized on the Ru(I) center.

Keywords: P ligands; metal radicals; non-redox ligands; one-electron oxidation; ruthenium.

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