title: Iron(II) complexes with redox-active tetrazene (RNNNNR) ligands.
abstract: This paper describes the redox chemistry of a tetrazene ligand on (beta-diketiminato)iron complexes. Addition of 1-adamantyl azide to an iron(I) source gives the tetrazene complex L(Me)Fe(AdNNNNAd), most likely through an imidoiron(III) intermediate. Spectroscopic, magnetic, crystallographic, and computational investigations of the tetrazene complex show that one unpaired spin occupies a primarily ligand-based orbital, and is antiferromagnetically coupled to a high-spin iron(II) ion to give an S = 3/2 ground state. Reversible single-electron reduction occurs at the ligand singly occupied molecular orbital (SOMO), affording a dianionic tetrazene ligand while leaving the metal oxidation state and spin state unchanged.
authors.affiliation: Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
authors.forename: Ryan E
authors.initials: RE
authors.lastname: Cowley
authors.forename: Eckhard
authors.initials: E
authors.lastname: Bill
authors.forename: Frank
authors.initials: F
authors.lastname: Neese
authors.forename: William W
authors.initials: WW
authors.lastname: Brennessel
authors.forename: Patrick L
authors.initials: PL
authors.lastname: Holland
mesh_terms: D001386:Azides / Q000737:chemistry*; D003198:Computer Simulation; D018360:Crystallography, X-Ray; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D008024:Ligands; D008280:Magnetics; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013696:Temperature
chemical_list: D001386:Azides; D005296:Ferrous Compounds; D008024:Ligands