From 0 to II in One‐Electron Steps: A Series of Ruthenium Complexes Supported by TropPPh2. Issue 39 (25th August 2016)

• Record Type: Journal Article
• Authors: Yang, Xiuxiu; Gianetti, Thomas L.; Harbort, Joshua; Wörle, Michael D.; Tan, Lilin; Su, Cheng‐Yong; Jurt, Pascal; Harmer, Jeffrey R.; Grützmacher, Hansjörg
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 39(2016)
• Page Start: 11999
• Page End: 12002
• Publication Date: 2016-08-25
• Subjects: metal radicals -- non-redox ligands -- one-electron oxidation -- P ligands -- ruthenium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201605687
• Languages: English
• ISSNs: 1433-7851

Abstract

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. Abstract : Easy as 0, 1, 2 : A series of ruthenium complexes with oxidation states n =0, +1, and +2 is described with [Ru(tropPPh2 )2 ] n of identical chemical composition but remarkably different structure. In the Ru I complex, the single unpaired electron is mainly localized on the metal center.