TY - JOUR
T1 - High-valent nonheme iron. Two distinct iron(IV) species derived from a common iron(II) precursor
AU - Jensen, Michael P.
AU - Costas, Miquel
AU - Ho, Raymond Y.N.
AU - Kaizer, József
AU - Mairata I Payeras, Antoni
AU - Münck, Eckard
AU - Que, Lawrence
AU - Ronde, Jan Uwe
AU - Stubna, Audria
N1 - Copyright:
Copyright 2008 Elsevier B.V., All rights reserved.
PY - 2005/8/3
Y1 - 2005/8/3
N2 - The reaction of [FeII(β-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 °C and above, 2-NCMe converts to a pale green species 3 (λmax = 753 nm, ε = 280 M-1 cm -1) in 90% yield, identified as [FeIV(O)(BPMCN)(NCCH 3)]2+ by comparison to other nonheme [Fe IV(O)(L)]2+ complexes. Below -55 °C in CH 2Cl2, 2 decays instead to form deep turquoise 4 (λmax = 656, 845 nm; ε = 4000, 3600 M-1 cm-1), formulated to be an unprecedented alkylperoxoiron(IV) complex [FeIV(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.
AB - The reaction of [FeII(β-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 °C and above, 2-NCMe converts to a pale green species 3 (λmax = 753 nm, ε = 280 M-1 cm -1) in 90% yield, identified as [FeIV(O)(BPMCN)(NCCH 3)]2+ by comparison to other nonheme [Fe IV(O)(L)]2+ complexes. Below -55 °C in CH 2Cl2, 2 decays instead to form deep turquoise 4 (λmax = 656, 845 nm; ε = 4000, 3600 M-1 cm-1), formulated to be an unprecedented alkylperoxoiron(IV) complex [FeIV(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.
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U2 - 10.1021/ja0438765
DO - 10.1021/ja0438765
M3 - Article
C2 - 16045338
AN - SCOPUS:23044479791
SN - 0002-7863
VL - 127
SP - 10512
EP - 10525
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 30
ER -