Jensen Michael P, Costas Miquel, Ho Raymond Y N, Kaizer József, Mairata i Payeras Antoni, Münck Eckard, Que Lawrence, Rohde Jan-Uwe, Stubna Audria
Department of Chemistry and the Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota 55455, USA.
J Am Chem Soc. 2005 Aug 3;127(30):10512-25. doi: 10.1021/ja0438765.
The reaction of [Fe(II)(beta-BPMCN)(OTf)2] (1, BPMCN = N,N'-bis(2-pyridylmethyl)-N,N'-dimethyl-trans-1,2-diaminocyclohexane) with tBuOOH at low-temperature yields alkylperoxoiron(III) intermediates 2 in CH2Cl2 and 2-NCMe in CH3CN. At -45 degrees C and above, 2-NCMe converts to a pale green species 3 (lambda(max) = 753 nm, epsilon = 280 M(-1) cm(-1)) in 90% yield, identified as [Fe(IV)(O)(BPMCN)(NCCH3)]2+ by comparison to other nonheme [Fe(IV)(O)(L)]2+ complexes. Below -55 degrees C in CH2Cl2, 2 decays instead to form deep turquoise 4 (lambda(max) = 656, 845 nm; epsilon = 4000, 3600 M(-1) cm(-1)), formulated to be an unprecedented alkylperoxoiron(IV) complex [Fe(IV)(BPMCN)(OH)(OOtBu)]2+ on the basis of Mössbauer, EXAFS, resonance Raman, NMR, and mass spectral evidence. The reactivity of 1 with tBuOOH in the two solvents reveals an unexpectedly rich iron(IV) chemistry that can be supported by the BPMCN ligand.
[Fe(II)(β - BPMCN)(OTf)₂]（1，BPMCN = N,N'-双(2 - 吡啶甲基)-N,N'-二甲基 - 反式 - 1,2 - 二氨基环己烷）在低温下与叔丁基过氧化氢（tBuOOH）反应，在二氯甲烷中生成烷基过氧铁(III)中间体2，在乙腈中生成2 - NCMe。在 - 45℃及以上温度时，2 - NCMe会转化为一种浅绿色物质3（λmax = 753 nm，ε = 280 M⁻¹ cm⁻¹），产率为90%，通过与其他非血红素[Fe(IV)(O)(L)]²⁺配合物比较，确定其为[Fe(IV)(O)(BPMCN)(NCCH₃)]²⁺。在二氯甲烷中低于 - 55℃时，2会分解形成深绿松石色物质4（λmax = 656、845 nm；ε = 4000、3600 M⁻¹ cm⁻¹），根据穆斯堡尔谱、扩展X射线吸收精细结构谱、共振拉曼光谱、核磁共振谱和质谱证据，推测其为一种前所未有的烷基过氧铁(IV)配合物[Fe(IV)(BPMCN)(OH)(OOtBu)]²⁺。1与tBuOOH在两种溶剂中的反应揭示了由BPMCN配体支持的、出乎意料丰富的铁(IV)化学性质。
