Facile and Reversible Formation of Iron(III)-Oxo-Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III)

被引:27
作者
Draksharapu, Apparao [1 ,2 ]
Rasheed, Waqas [1 ,2 ]
Klein, Johannes E. M. N. [1 ,2 ]
Que, Lawrence, Jr. [1 ,2 ]
机构
[1] Univ Minnesota, Dept Chem, 207 Pleasant St SE, Minneapolis, MN 55455 USA
[2] Univ Minnesota, Ctr Met Biocatalysis, Minneapolis, MN 55455 USA
基金
美国国家卫生研究院;
关键词
cerium; spin crossover; electron transfer; iron; water oxidation; EXCHANGE-ENHANCED REACTIVITY; COUPLED ELECTRON-TRANSFER; WATER OXIDATION; CRYSTAL-STRUCTURE; IRON COMPLEXES; MOLECULAR CATALYSTS; 2-STATE REACTIVITY; ACTIVATION; CHEMISTRY; LIGAND;
D O I
10.1002/anie.201704322
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Ceric ammonium nitrate (CAN) or Ce-IV(NH4)(2)- (NO3)(6) is often used in artificial water oxidation and generally considered to be an outer-sphere oxidant. Herein we report the spectroscopic and crystallographic characterization of [(N4Py) Fe-III-O-Ce-IV(OH2)(NO3)(4)](+) (3), a complex obtained from the reaction of [(N4Py) FeII(NCMe)](2+) with 2 equiv CAN or [(N4Py) Fe-IV=O](2+) (2) with CeIII(NO3)(3) in MeCN. Surprisingly, the formation of 3 is reversible, the position of the equilibrium being dependent on the MeCN/water ratio of the solvent. These results suggest that the Fe-IV and Ce-IV centers have comparable reduction potentials. Moreover, the equilibrium entails a change in iron spin state, from S = 1 Fe-IV in 2 to S = 5/2 in 3, which is found to be facile despite the formal spin-forbidden nature of this process. This observation suggests that Fe-IV=O complexes may avail of reaction pathways involving multiple spin states having little or no barrier.
引用
收藏
页码:9091 / 9095
页数:5
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