High-Valent Nonheme Iron. Two Distinct Iron(IV) Species Derived from a Common Iron(II) Precursor
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- 作者：Michael P. Jensen ; Miquel Costas ; Raymond Y. N. Ho ; Jó ; zsef Kaizer ; Antoni Mairata i Payeras ; Eckard Mü ; nck ; Lawrence Que ; Jr. ; Jan-Uwe Rohde ; and Audria Stubna
- 刊名：Journal of the American Chemical Society
- 出版年：2005
- 出版时间：August 3, 2005
- 年：2005
- 卷：127
- 期：30
- 页码：10512 - 10525
- 全文大小：343K
- 年卷期：v.127,no.30(August 3, 2005)
- ISSN：1520-5126
文摘
The reaction of [FeII(
-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 2in CH2Cl2 and 2-NCMe in CH3CN. At -45 
C and above, 2-NCMe converts to a pale green species 3 (
max= 753 nm, 
= 280 M-1 cm-1) in 90% yield, identified as [FeIV(O)(BPMCN)(NCCH3)]2+ by comparison toother nonheme [FeIV(O)(L)]2+ complexes. Below -55 C in CH2Cl2, 2 decays instead to form deep turquoise4 (max = 656, 845 nm; = 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, andmass spectral evidence. The reactivity of 1 with tBuOOH in the two solvents reveals an unexpectedly richiron(IV) chemistry that can be supported by the BPMCN ligand.
-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 2in CH2Cl2 and 2-NCMe in CH3CN. At -45 C and above, 2-NCMe converts to a pale green species 3 (max= 753 nm, = 280 M-1 cm-1) in 90% yield, identified as [FeIV(O)(BPMCN)(NCCH3)]2+ by comparison toother nonheme [FeIV(O)(L)]2+ complexes. Below -55 C in CH2Cl2, 2 decays instead to form deep turquoise4 (max = 656, 845 nm; = 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, andmass spectral evidence. The reactivity of 1 with tBuOOH in the two solvents reveals an unexpectedly richiron(IV) chemistry that can be supported by the BPMCN ligand.