Triamidoamine complexes of chromium(IH) and chromium(IV)

Treatment of [CrCl3(THF)(3)] with slightly more than 1 equiv of Li-3(N3N) [(N3N)(3-) = ((Me3SiNCH2CH2)(3)N)(3-)] affords. the triamidoamine complex [Cr(N3N)] (1) in 75% yield. 1 is oxidized by PhICl2, CuCl2, or AgCl to give the chromium(IV) complex [Cr(N3N)Cl] (2) in moderate yields. Alternatively, complex 2 is obtained directly from [CrCl3(THF)(3)] in 50% yield after treatment with 0.5 equiv of Li-3(N3N). Both compounds are high-spin complexes bearing three and two impaired electrons, respectively. Their molecular structures are described revealing a trigonal monopyramidal and trigonal. bipyramidal coordination geometry of the chromium center, respectively.