Iron(II) Complexes with Redox-Active Tetrazene (RNNNNR) Ligands
作者： Ryan E. Cowley , Eckhard Bill , Frank Neese , William W. Brennessel , Patrick L. Holland
DOI: 10.1021/IC900001Y
关键词: Chemistry 、 Molecular orbital 、 Redox 、 Azide 、 Molecule 、 Spin states 、 Oxidation state 、 Tetrazene 、 Ligand 、 Crystallography 、 Photochemistry
摘要: This paper describes the redox chemistry of a tetrazene ligand on (beta-diketiminato)iron complexes. Addition 1-adamantyl azide to an iron(I) source gives complex L(Me)Fe(AdNNNNAd), most likely through imidoiron(III) intermediate. Spectroscopic, magnetic, crystallographic, and computational investigations show that one unpaired spin occupies primarily ligand-based orbital, is antiferromagnetically coupled high-spin iron(II) ion give S = 3/2 ground state. Reversible single-electron reduction occurs at singly occupied molecular orbital (SOMO), affording dianionic while leaving metal oxidation state unchanged.
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