Mono- and Dinuclear Neutral and Cationic Iron(II) Compounds Supported by an Amidinato-diolefin Ligand: Characterization and Catalytic Application

A new amidinato-diolefin ligand is presented along with its sodium salt as a starting point for the preparation of iron­(II) compounds. Rational synthetic approaches to cationic and dinuclear iron species have been established and allowed for the first isolation of an amidinato stabilized cationic Fe species. The versatility of the potentially tetradentate ligand system is mirrored by structural authentification of three different binding modes. These include rare examples of Fe­(II)–olefin interactions in neutral compounds. A set of iron compounds was shown to be active as precatalysts in the synthesis of poly silylethers by dehydrogenative alcoholysis of PhSiH3. The most active catalyst was generated from a dinuclear iron compound. Characterization techniques include NMR, IR, and Mössbauer spectroscopy, single crystal X-ray analysis, magnetic susceptibility measurements, and mass spectrometry.