分别使用它们与叔丁基过氧化氢(t-BuOOH) 在−40 °C温度下及二氯甲烷溶剂中进行反应。通过ESI-MS质谱、可见吸收光谱变化和1H NMR 化学位移的变化检测,它们皆可快速从不稳定的Fe(III)-烷基过氧中间体,即Fe(III)-O(H)OR (2),导致氧-氧键均裂成为四价铁氧代(Fe(IV)=O)卟啉(3)错合物。 作者还从[t-
Non-heme Fe(IV)-oxo intermediates. Acc. Chem. Res. 2007; 40:484-492. [PubMed: 17542550]C. Krebs, D. Galonic Fujimori, C.T. Walsh, J.M. Bollinger Jr., Non-heme Fe(IV)- oxo intermediates, Acc. Chem. Res. 40 (2007) 484-492....
中国科学院上海有机化学研究所的周佳海课题组与北卡罗来纳州立大学的张玮成课题组合作,解析了高分辨率蓝藻链球菌来源的ScoE与底物及推测中间体的复合物晶体结构,同时卡内基梅隆大学郭以嵩课题组利用Mössbauer光谱学表征了Fe(IV)-oxo物种...
人们普遍认为，在烷烃C-H键的官能团化过程中，Fe-oxo分子会通过生成自由基中间体来引发氢原子转移反应，随后可能经历自由基回弹、解离、去饱和等多样化的反应路径。然而，最新研究发现，在某些Fe-oxo相关的催化反应中，自由基并非静态中间体，而是可能以动态方式存在，并动态调控自由基回弹与解离反应的选择性。但目前，...
Through the oxidative decarboxylation of αKG, a reactive Fe(IV)-oxo intermediate is generated to activate a selective aliphatic C–H bond, which is normally difficult to cleave due to high bond-dissociation energy, and then oxidative products are generated following radical recombination. Unlike ...
要点2.此外,弱化的配位场降低Fe=O σ*轨道能量,促进高价Fe-oxo亲电性σ进攻双酚A,使得降解速率提高41.6倍。 这项研究展示二级配位球工程是可靠的策略,解决SAC分子的活性-稳定性权衡问题,为开发环境催化剂提供帮助。 Chen, T., Z...
Synchrotron-based nuclear resonance vibrational spectroscopy is used to characterize the reactive Fe(iv)=O intermediate of the halogenase SyrB2; the substrate directs the orientation of this intermediate, presenting specific frontier molecular orbitals t
DFT calculations indicate the Fe(IV) oxo mechanism will be the preferred route of these two possibilities. We further show via kinetic profiling and EPR studies that catalyst activation follows a radical pathway, which is initiated by hydrolysis of PhCO 3 t Bu to t BuOOH. Overall, the ...
首先以[(H2O)2Fe(III) (μO)2Fe(III) (H2O)2]2+超框架簇沉积在沸石孔中,在H2O2的作用下形成Fe(III)-oxo及Fe(IV)-oxo络合物,这两种络合物对甲烷解离具有明显的催化效应。这两种Fe络合剂含有三个位点,所有位点都能够促进甲烷中的第一个C-H键断裂,C-H键断裂后会形成MeOH和MeOOH。反应介质中的H2O2氧化剂...
prototypical Fe(II)- and α-KG-dependent dioxygenase mechanism reminiscent of TauD and AtsK, wherein decarboxylative oxidation of α-KG is coupled to the formation of an Fe(IV)-oxo intermediate that serves as the strong oxidizing agent for hydrogen abstraction of the prime substrate (...