Origin of the Enhanced Reactivity of μ-Nitrido-Bridged Diiron(IV)-Oxo Porphyrinoid Complexes over Cytochrome P450 Compound I
作者： Matthew G Quesne , Dhurairajan Senthilnathan , Devendra Singh , Devesh Kumar , Pascale Maldivi
关键词: Density functional theory 、 Phthalocyanine 、 Reactivity (chemistry) 、 Catalysis 、 Photochemistry 、 Activation energy 、 Hydroxylation 、 Porphyrin 、 Hydrogen atom abstraction 、 Chemistry
摘要: μ-Nitrido-bridged diiron porphyrins and phthalocyanines are known to be efficient oxidants that able oxidize some of the strongest C–H bonds in nature, such as one methane. The origin their catalytic efficiency is poorly understood, order gain insight into structural electronic features this chemical system, we performed a detailed systematic study properties reactivities using density functional theory. Our work shows μ-nitrido-bridged highly active oxidants, which react with methane very low reaction barriers rate-determining hydrogen-atom-abstraction step. Furthermore, porphyrin phthalocyanine complexes free energy activation more than 10 kcal mol–1 lower found for cytochrome P450 Compound I, most hydroxylating agents Nature. We have analyzed ...
acs.org
core.ac.uk
manchester.ac.uk参考文章(102)
John T. Groves, Models and Mechanisms of Cytochrome P450 Action Cytochrome P450. pp. 1- 43 ,(2005) , 10.1007/0-387-27447-2_1
Cristina S. Porro, Michael J. Sutcliffe, Sam P. de Visser, Quantum mechanics/molecular mechanics studies on the sulfoxidation of dimethyl sulfide by compound i and compound 0 of cytochrome p450: Which is the better oxidant Journal of Physical Chemistry A. ,vol. 113, pp. 11635- 11642 ,(2009) , 10.1021/JP9023926
Margareta R. A. Blomberg, Tomasz Borowski, Fahmi Himo, Rong-Zhen Liao, Per E. M. Siegbahn, Quantum chemical studies of mechanisms for metalloenzymes. Chemical Reviews. ,vol. 114, pp. 3601- 3658 ,(2014) , 10.1021/CR400388T
Julie Colin, Ben Wiseman, Jacek Switala, Peter C. Loewen, Anabella Ivancich, Distinct role of specific tryptophans in facilitating electron transfer or as [Fe(IV)=O Trp(*)] intermediates in the peroxidase reaction of Bulkholderia pseudomallei catalase-peroxidase: a multifrequency EPR spectroscopy investigation. Journal of the American Chemical Society. ,vol. 131, pp. 8557- 8563 ,(2009) , 10.1021/JA901402V
P. Jeffrey Hay, Willard R. Wadt, Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals Journal of Chemical Physics. ,vol. 82, pp. 299- 310 ,(1985) , 10.1063/1.448975
A.B. Sorokin, E.V. Kudrik, L.X. Alvarez, P. Afanasiev, J.M.M. Millet, D. Bouchu, Oxidation of methane and ethylene in water at ambient conditions Catalysis Today. ,vol. 157, pp. 149- 154 ,(2010) , 10.1016/J.CATTOD.2010.02.007
J. T. Groves, The bioinorganic chemistry of iron in oxygenases and supramolecular assemblies Proceedings of the National Academy of Sciences of the United States of America. ,vol. 100, pp. 3569- 3574 ,(2003) , 10.1073/PNAS.0830019100
J. Rittle, M. T. Green, Cytochrome P450 Compound I: Capture, Characterization, and C-H Bond Activation Kinetics Science. ,vol. 330, pp. 933- 937 ,(2010) , 10.1126/SCIENCE.1193478
Aidan R. McDonald, Lawrence Que, High-valent nonheme iron-oxo complexes: Synthesis, structure, and spectroscopy Coordination Chemistry Reviews. ,vol. 257, pp. 414- 428 ,(2013) , 10.1016/J.CCR.2012.08.002
James M. Mayer, HYDROGEN ATOM ABSTRACTION BY METAL-OXO COMPLEXES : UNDERSTANDING THE ANALOGY WITH ORGANIC RADICAL REACTIONS Accounts of Chemical Research. ,vol. 31, pp. 441- 450 ,(1998) , 10.1021/AR970171H