State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, PR China.
Inorg Chem. 2013 May 20;52(10):5906-13. doi: 10.1021/ic400053g. Epub 2013 May 8.
A diversified reactivity of the mononuclear bis(amidinato)iron(II) complex [Fe(MesC(NPr(i))2)2] (1) toward oxidizing reagents has been disclosed. The bis(amidinato)iron(II) complex was synthesized from the reaction of [Fe(Mes)2]2 with 4 equiv of diisopropyl carbodiimide in good yield. Treatment of 1 with 1 equiv of benzyl chloride gives the high-spin ferric complex [FeCl(MesC(NPr(i))2)2] (2), with 0.25 equiv of S8 affords the sulfur-insertion product [Fe(MesC(NPr(i))(NPr(i)S))2] (3), with 1 equiv of 3,5-dimethylphenyl azide or phenyl azide yields nitrene-insertion product [Fe(MesC(NPr(i))2)(Pr(i)NC(Mes)N(Pr(i))NAr)] (Ar = 3,5-dimethylphenyl, 4a; phenyl, 4b), and with 1 equiv of oxo-transfer reagent, trimethylamine oxide or 2,6-dichloropyridine oxide, generates the oxo-bridged diferric complex [(MesC(NPr(i))2)2FeOFe(MesC(NPr(i))2)2] (5). Complexes 1-3, 4a, and 5 have been characterized by (1)H NMR, UV-vis, IR, elemental analysis, and single-crystal X-ray diffraction studies. The formations of these unusual sulfur- and nitrene-insertion products 3, 4a, and 4b, can be explained by the sequential redox reaction between 1 and the oxidants, followed by migratory insertion steps.
单核双(脒基)铁(II)配合物[Fe(MesC(NPr(i))2)2]（1）对氧化试剂表现出多样化的反应性。该双(脒基)铁(II)配合物由[Fe(Mes)2]2与4当量的二异丙基碳二亚胺反应，以良好的产率得到。用 1 当量的苄基氯处理 1 得到高自旋的三氯化铁配合物[FeCl(MesC(NPr(i))2)2]（2），用 0.25 当量的 S8 得到硫插入产物[Fe(MesC(NPr(i))(NPr(i)S))2]（3），用 1 当量的 3,5-二甲基苯基叠氮化物或苯基叠氮化物得到氮烯插入产物[Fe(MesC(NPr(i))2)(Pr(i)NC(Mes)N(Pr(i))NAr)]（Ar = 3,5-二甲基苯基，4a；苯基，4b），用 1 当量的氧转移试剂，三甲胺氧化物或 2,6-二氯吡啶氧化物，生成氧桥联双铁配合物[(MesC(NPr(i))2)2FeOFe(MesC(NPr(i))2)2]（5）。配合物 1-3、4a 和 5 已通过（1）H NMR、UV-vis、IR、元素分析和单晶 X 射线衍射研究进行了表征。这些不寻常的硫和氮烯插入产物 3、4a 和 4b 的形成可以通过 1 与氧化剂之间的顺序氧化还原反应来解释，然后是迁移插入步骤。
