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Wang, Bin,Lee, Yong-Min,Clé,mancey, Martin,Seo, Mi Sook,Sarangi, Ritimukta,Latour, Jean-Marc,Nam, Wonwoo American Chemical Society 2016 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.138 No.7
<P>Mononuclear nonheme high-spin iron(III)-acylperoxo complexes bearing an N-methylated cyclam ligand were synthesized, spectroscopically characterized, and investigated in olefin epoxidation and alkane hydroxylation reactions. In the epoxidation of olefins, epoxides were yielded as the major products with high stereo-, chemo-, and enantioselectivities; cis- and trans-stilbenes were oxidized to cis- and trans-stilbene oxides, respectively. In the epoxidation of cyclohexene, cyclohexene oxide was formed as the major product with a kinetic isotope effect (KIE) value of 1.0, indicating that nonheme iron(III)-acylperoxo complexes prefer C=C epoxidation to allylic C-H bond epoxidation by chiral iron(III)-acylperoxo complexes afforded epoxides with high enantioselectivity, suggesting that iron(III)acylperoxo species, not high-valent iron-oxo species, are the epoxidizing agent. In alkane hydroxylation reactions, iron(III)acylperoxo complexes hydroxylated C-H bonds as strong as those in cyclohexane at -40 degrees C, wherein (a) alcohols were yielded as the major products with high regio- and stereoselectivities, (b) activation of C-H bonds by the iron(III)-acylperoxo species was the rate -determining step with a large KIE value and good correlation between reaction rates and bond dissociation energies of alkanes, and (c) the oxygen atom in the alcohol product was from the iron(III)-acylperoxo species, not from molecular oxygen. In isotopically labeled water ((H2O)-O-13) experiments, incorporation of 180 from (H2O)-O-18 into oxygenated products was not observed in the epoxidation and hydroxylation reactions. On the basis of mechanistic studies, we conclude that mononuclear nonheme high-spin iron(III)-acylperoxo complexes are strong oxidants capable of oxygenating hydrocarbons prior to their conversion into iron-oxo species via O-O bond cleavage.</P>
Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex
Hong, Seungwoo,Lu, Xiaoyan,Lee, Yong-Min,Seo, Mi Sook,Ohta, Takehiro,Ogura, Takashi,Clé,mancey, Martin,Maldivi, Pascale,Latour, Jean-Marc,Sarangi, Ritimukta,Nam, Wonwoo American Chemical Society 2017 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.139 No.41
<P>A mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [Fe<SUP>V</SUP>(NTs)(TAML)]<SUP>−</SUP> (<B>1</B>), was oxidized by one-electron oxidants, affording formation of an iron(V)-imido TAML cation radical species, [Fe<SUP>V</SUP>(NTs)(TAML<SUP>+•</SUP>)] (<B>2</B>); <B>2</B> is a diamagnetic (<I>S</I> = 0) complex, resulting from the antiferromagnetic coupling of the low-spin iron(V) ion (<I>S</I> = 1/2) with the one-electron oxidized ligand (TAML<SUP>+•</SUP>). <B>2</B> is a competent oxidant in C–H bond functionalization and nitrene transfer reaction, showing that the reactivity of <B>2</B> is greater than that of <B>1</B>.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2017/jacsat.2017.139.issue-41/jacs.7b08161/production/images/medium/ja-2017-081612_0005.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja7b08161'>ACS Electronic Supporting Info</A></P>
Lu, Xiaoyan,Li, Xiao-Xi,Seo, Mi Sook,Lee, Yong-Min,Clé,mancey, Martin,Maldivi, Pascale,Latour, Jean-Marc,Sarangi, Ritimukta,Fukuzumi, Shunichi,Nam, Wonwoo American Chemical Society 2019 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.141 No.1
<P>A mononuclear nonheme iron(IV)-amido complex bearing a tetraamido macrocyclic ligand, [(TAML)Fe<SUP>IV</SUP>(NHTs)]<SUP>−</SUP> (<B>1</B>), was synthesized via a hydrogen atom (H atom) abstraction reaction of an iron(V)-imido complex, [(TAML)Fe<SUP>V</SUP>(NTs)]<SUP>−</SUP> (<B>2</B>), and fully characterized using various spectroscopies. We then investigated (1) the p<I>K</I><SUB>a</SUB> of <B>1</B>, (2) the reaction of <B>1</B> with a carbon-centered radical, and (3) the H atom abstraction reaction of <B>1</B>. To the best of our knowledge, the present study reports for the first time the synthesis and chemical properties/reactions of a high-valent iron(IV)-amido complex.</P> [FIG OMISSION]</BR>
Seo, Mi Sook,Kim, Nam Hee,Cho, Kyung-Bin,So, Jeong Eun,Park, Seon Kyung,Clé,mancey, Martin,Garcia-Serres, Ricardo,Latour, Jean-Marc,Shaik, Sason,Nam, Wonwoo Royal Society of Chemistry 2011 Chemical science Vol.2 No.6
<P>A highly reactive mononuclear nonheme iron(<SMALL>IV</SMALL>)-oxo complex with a low-spin (<I>S</I> = 1) triplet ground state in both C–H bond activation and oxo transfer reactions is reported; this nonheme iron(<SMALL>IV</SMALL>)-oxo complex is more reactive than an iron(<SMALL>IV</SMALL>)-oxo porphyrin π-cation radical (<I>i.e.</I>, a model of cytochrome P450 compound I) and is the most reactive species in kinetic studies among nonheme iron(<SMALL>IV</SMALL>)-oxo complexes reported so far. DFT calculations support the experimental results with extremely low activation barriers in the C–H bond activation of cyclohexane and 1,4-cyclohexadiene. The DFT calculations reveal that the <I>S</I> = 1 state is set up to easily lead to the highly reactive <I>S</I> = 2 high-spin iron(<SMALL>IV</SMALL>)-oxo species.</P> <P>Graphic Abstract</P><P>A mononuclear nonheme iron(<SMALL>IV</SMALL>)-oxo complex with a ground low-spin (<I>S</I> = 1) triplet state is found to be a powerful oxidant in both C–H bond activation and oxo transfer reactions and more reactive than a cytochrome P450 model compound I. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c1sc00062d'> </P>
Hong, Seungwoo,Wang, Bin,Seo, Mi Sook,Lee, Yong‐,Min,Kim, Myoung Jin,Kim, Hyung Rok,Ogura, Takashi,Garcia‐,Serres, Ricardo,Clé,mancey, Martin,Latour, Jean‐,Marc,Nam, Wonwoo WILEY‐VCH Verlag 2014 Angewandte Chemie Vol.126 No.25
<P><B>Abstract</B></P><P>High‐spin iron(III) iodosylarene complexes bearing an N‐methylated cyclam ligand are synthesized and characterized using various spectroscopic methods. The nonheme high‐spin iron(III) iodosylarene intermediates are highly reactive oxidants capable of activating strong CH bonds of alkanes; the reactivity of the iron(III) iodosylarene intermediates is much greater than that of the corresponding iron(IV) oxo complex. The electrophilic character of the iron(III) iodosylarene complexes is demonstrated in sulfoxidation reactions.</P>