非血红素氧合铁(IV)配合物与铈(III)制备铁(III)-氧-铈(IV)加合物的简便和可逆方法。
Facile and Reversible Formation of Iron(III)-Oxo-Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III).
机构信息
Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN, 55455, USA.
出版信息
Angew Chem Int Ed Engl. 2017 Jul 24;56(31):9091-9095. doi: 10.1002/anie.201704322. Epub 2017 Jun 27.
Abstract
Ceric ammonium nitrate (CAN) or Ce (NH ) (NO ) 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 -O-Ce (OH )(NO ) ] (3), a complex obtained from the reaction of [(N4Py)Fe (NCMe)] with 2 equiv CAN or [(N4Py)Fe =O] (2) with Ce (NO ) 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 and Ce centers have comparable reduction potentials. Moreover, the equilibrium entails a change in iron spin state, from S=1 Fe 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 =O complexes may avail of reaction pathways involving multiple spin states having little or no barrier.
摘要
硝酸铈铵（CAN）或 Ce（NH ）（NO ）通常用于人工水氧化，通常被认为是一种外壳氧化剂。在此，我们报告了[(N4Py)Fe-O-Ce(OH)(NO ) ]（3）的光谱和晶体化学特征，该配合物是通过[(N4Py)Fe(NCMe)]与 2 当量 CAN 或[(N4Py)Fe=O]（2）与 Ce(NO )在 MeCN 中的反应得到的。令人惊讶的是，3 的形成是可逆的，平衡位置取决于溶剂的 MeCN/水比。这些结果表明，Fe 和 Ce 中心具有相当的还原电位。此外，平衡伴随着铁自旋态的变化，从 2 中的 S=1 Fe 变为 3 中的 S=5/2，尽管这个过程在形式上是自旋禁阻的，但发现这个变化很容易发生。这一观察结果表明，Fe=O 配合物可能利用涉及多个自旋态的反应途径，这些自旋态几乎没有或没有障碍。
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