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学科主题: 物理化学
题名: Nonheme Iron Oxidant Formed in the Presence of H2O2 and Acetic Acid Is the Cyclic Ferric Peracetate Complex, Not a Perferryloxo Complex
作者: Wang, Yong1;  Janardanan, Deepa2, 3;  Usharani, Dandamudi2, 3;  Han, Keli1;  Que, Lawrence, Jr.4, 5;  Shaik, Sason2, 3
通讯作者: 王永 ;  Lawrence Que ;  Jr. ;  Sason Shaik
关键词: nonheme iron ;  C-H activation ;  density functional calculations ;  oxometal ;  O-O homolysis
刊名: ACS CATALYSIS
发表日期: 2013-06-01
DOI: 10.1021/cs400134g
卷: 3, 期:6, 页:1334-1341
收录类别: SCI
合作性质: 
文章类型: Article
部门归属: 11
项目归属: 1101
产权排名: 待补充
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical
资助者: 1,1
研究领域[WOS]: Chemistry
英文摘要: Oxidative C-H bond activation, is a transformation of fundamental and practical interest, particularly if it can be carried out with high regio- and enantioselectivity. With nonheme iron oxygenases as inspiration (e.g., the Rieske oxygenases), a family of biomimetic nonheme iron complexes has been found to catalyze hydrocarbon oxidations by H2O2 via a postulated Fe-V(O)(OH) oxidant. Of particular interest is the Fe(S,S-PDP) catalyst discovered by White that, in the presence of acetic acid as an additive, performs selective C-H bond activation, even in complex organic molecules. The corresponding Fe-V(O)(OAc) species has been suggested as the key oxidant. We have carried out DFT studies to assess the viability of such an oxidant and discovered an alternative formulation. Theory reveals that the barrier for the formation of the putative Fe-V(O)(OAc) oxidant is too high for it to be feasible. Instead, a much lower barrier is found for the formation of a [(S,S-PDP)Fe-III(kappa(2)-peracetate)] species. In the course of C-H activation, this complex undergoes O-O bond homolysis to become a transient [(S,S-PDP)Fe-IV(O)(AcO center dot)] species that performs the efficient hydroxylation of alkanes. Thus, the acetic acid additive alters completely the nature of the high-valent oxidant, which remains disguised in the cyclic structure. This new mechanism can rationalize the many experimental observations associated with the oxidant formed in the presence of acetic acid, including the S = 1/2 EPR signal associated with the oxidant. These results further underscore the rich multioxidant scenario found in the mechanistic landscape for nonheme iron catalysts.
关键词[WOS]: DENSITY-FUNCTIONAL THERMOCHEMISTRY ;  ZETA VALENCE QUALITY ;  GAUSSIAN-BASIS SETS ;  O BOND-CLEAVAGE ;  C-H ;  IPSO-HYDROXYLATION ;  HYDROGEN-PEROXIDE ;  BENZOIC-ACIDS ;  COMPOUND-I ;  ATOMS LI
语种: 英语
原文出处: 查看原文
WOS记录号: WOS:000320298800028
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/119426
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
2.Hebrew Univ Jerusalem, Inst Chem, IL-91904 Jerusalem, Israel
3.Hebrew Univ Jerusalem, Lise Meitner Minerva Ctr Computat Quantum Chem, IL-91904 Jerusalem, Israel
4.Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA
5.Univ Minnesota, Ctr Met Biocatalysis, Minneapolis, MN 55455 USA

Recommended Citation:
Wang, Yong,Janardanan, Deepa,Usharani, Dandamudi,et al. Nonheme Iron Oxidant Formed in the Presence of H2O2 and Acetic Acid Is the Cyclic Ferric Peracetate Complex, Not a Perferryloxo Complex[J]. ACS CATALYSIS,2013,3(6):1334-1341.
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