Two-Coordinate Iron(I) Complex [Fe{N(SiMe sub(3)) sub(2)} sub(2)] super(-): Synthesis, Properties, and Redox Activity

First-row two-coordinate complexes are attracting much interest. Herein, we report the high-yield isolation of the linear two-coordinate iron(I) complex salt [K(L)][Fe{N(SiMe sub(3)) sub(2)} sub(2)] (L=18-crown-6 or crypt-222) through the reduction of either [Fe{N(SiMe sub(3)) sub(2)} sub(2)] or its three-coordinate phosphine adduct [Fe{N(SiMe sub(3)) sub(2)} sub(2)(PCy sub(3))]. Detailed characterization is gained through X-ray diffraction, variable-temperature NMR spectroscopy, and magnetic susceptibility studies. One- and two-electron oxidation through reaction with I sub(2) is further found to afford the corresponding iodo iron(II) and diiodo iron(III) complexes.Original Abstract: Eisen und I sub(2) - I, II, III: Der lineare zweifach koordinierte Eisen(I)-Komplex [Fe{N(SiMe sub(3)) sub(2)} sub(2)] super(-) entsteht in hoher Ausbeute durch Reduktion von [Fe{N(SiMe sub(3)) sub(2)} sub(2)] oder [Fe{N(SiMe sub(3)) sub(2)} sub(2)(PCy sub(3))]. Ein- und Zwei-Elektronen-Oxidationen mit I sub(2) liefern den entsprechenden Iodoeisen(II)- bzw. Diiodeisen(III)-Komplex.