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9月, 2014の投稿を表示しています

Status of Reactive Non-Heme Metal–Oxygen Intermediates in Chemical and Enzymatic Reaction

Kallol Ray * † , Florian Felix Pfaff † , Bin Wang ‡ , and Wonwoo Nam * ‡ † Department of Chemistry, Humboldt-Universität zu Berlin , 12489 Berlin, Germany ‡ Department of Chemistry and Nano Science, Ewha Womans University , Seoul 120-750, Korea J. Am. Chem. Soc. , Article ASAP DOI: 10.1021/ja507807v Publication Date (Web): September 12, 2014 Copyright © 2014 American Chemical Society wwnam@ewha.ac.kr , kallol.ray@chemie.hu-berlin.de Abstract

Spectroscopic Capture and Reactivity of a Low-Spin Cobalt(IV)-Oxo Complex Stabilized by Binding Redox-Inactive Metal Ions†

Abstract High-valent cobalt-oxo intermediates are proposed as reactive intermediates in a number of cobalt-complex-mediated oxidation reactions. Herein we report the spectroscopic capture of low-spin ( S =1/2) Co IV -oxo species in the presence of redox-inactive metal ions, such as Sc 3+ , Ce 3+ , Y 3+ , and Zn 2+ , and the investigation of their reactivity in C H bond activation and sulfoxidation reactions. Theoretical calculations predict that the binding of Lewis acidic metal ions to the cobalt-oxo core increases the electrophilicity of the oxygen atom, resulting in the redox tautomerism of a highly unstable [(TAML)Co III (O . )] 2−  species to a more stable [(TAML)Co IV (O)(M n + )] core. The present report supports the proposed role of the redox-inactive metal ions in facilitating the formation of high-valent metal–oxo cores as a necessary step for oxygen evolution in chemistry and biology. Seungwoo Hong, Florian F. Pfaff, Eunji Kwon, Yong Wang, Mi-Sook Seo, Eck...

Oxygen-Atom Transfer Reactivity of Axially Ligated Mn(V)–Oxo Complexes: Evidence for Enhanced Electrophilic and Nucleophilic Pathways

チオエーテルの置換基で反応機構が変わるそうです。 Heather M. Neu   † ,  Tzuhsiung Yang   † ,  Regina A. Baglia   † ,  Timothy H. Yosca   § ,  Michael T. Green   * § , Matthew G. Quesne   ‡ ,  Sam P. de Visser   * ‡ , and  David P.  Goldberg   * † †  Department of Chemistry,  The Johns Hopkins University , Baltimore, Maryland 21218,  United States §  Department of Chemistry,  Pennsylvania State University , University Park, Pennsylvania 16802,  United States ‡  The Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science,  The University of Manchester , 131 Princess Street, Manchester M1 7DN,  United Kingdom J. Am. Chem. Soc. , Article ASAP DOI:  10.1021/ja507177h Publication Date (Web): September 19, 2014 Copyright © 2014 American Chemical Society dpg@jhu.edu ,  mtg10@psu.edu ,  sam.devisser@manchester.ac.uk ACS...

Direct Observation of a Nonheme Iron(IV)–Oxo Complex That Mediates Aromatic C–F Hydroxylation

Sumit Sahu   † ,  Matthew G. Quesne   ‡ ,  Casey G. Davies   § ,  Maximilian Dürr   ∥ ,  Ivana Ivanović-Burmazović   ∥ ,  Maxime A. Siegler   † ,  Guy N. L. Jameson   * § ,  Sam P. de Visser   * ‡ , and  David P. Goldberg   * † †  Department of Chemistry,  The Johns Hopkins University , 3400 North Charles Street, Baltimore, Maryland 21218,  United States ‡  Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science,  The University of Manchester , 131 Princess Street, Manchester M1 7DN,  United Kingdom §  Department of Chemistry & MacDiarmid Institute for Advanced Materials and Nanotechnology,  University of Otago , P.O. Box 56, Dunedin 9054,  New Zealand ∥  Department of Chemistry and Pharmacy,  University of Erlangen-Nürnberg , 91058 Erlangen,  Germany J. Am. Chem. Soc. , Article ASAP ...

Influence of Ligand Flexibility on the Electronic Structure of Oxidized NiIII-Phenoxide Complexe

  Inorganic Chemistry: Latest Articles (ACS Publications) by Minoru Kawai, Takahide Yamaguchi, Shigeyuki Masaoka, Fumito Tani, Takamitsu Kohzuma, Linus Chiang, Tim Storr, Kaoru Mieda, Takashi Ogura, Robert K. Szilagyi and Yuichi Shimazaki  /  11h  //  keep unread  //  hide  //  preview Inorganic Chemistry DOI: 10.1021/ic501181k

How calcium affects oxygen formation

先日のNature Chem. のペーパーの、解説記事です。 How calcium affects oxygen formation    p495 Calcium is an essential component of the catalyst that forms oxygen from water during photosynthesis. It seems that part of calcium's job is to enable the release of oxygen from this catalyst. Davide Lionetti, Theodor Agapie doi: 10.1038/nature13753 Article:  http://forcast.emailalert.jp/c/alqsan5CsxoItMaE

Development of a SO3H-Functionalized UiO-66 Metal–Organic Framework by Postsynthetic Modification and Studies of Its Catalytic Activities (pages 4268–4272)

Yi Luan, Nannan Zheng, Yue Qi, Jie Yu and Ge Wang Article first published online: 21 AUG 2014 | DOI: 10.1002/ejic.201402509 A novel metal–organic framework UiO-66-NH 2 -derived Brønsted acid catalyst is synthesized by employing a postsynthetic modification strategy under mild conditions. Acetalization and benzimidazole formation are evaluated to demonstrate the high reactivity and selectivity of the nanoscaled UiO-66-NH-RSO 3 H catalyst. Abstract Full Article (HTML) Enhanced Article (HTML) PDF(2121K) References Supporting Information Request Permissions

You have full text access to this contentBOX Ligands in Biomimetic Copper-Mediated Dioxygen Activation: A Hemocyanin Model (pages 4660–4676)

Adam Walli, Sebastian Dechert, Matthias Bauer, Serhiy Demeshko and Franc Meyer Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201402378 A series of bis(oxazoline)-copper(I) complexes reversibly bind dioxygen to yield biomimetic μ-η 2 :η 2 -peroxo-dicopper(II) species, which represent new functional hemocyanin models. Their kinetics of formation have been studied under cryo conditions, and the complexes have been isolated as surprisingly stable solids. All were investigated by a variety of methods, both in solution and in the solid state. Abstract Full Article (HTML) Enhanced Article (HTML) PDF(4392K) References Supporting Information Request Permissions

X-ray Emission Spectroscopy: A Spectroscopic Measure for the Determination of NO Oxidation State in Fe-NO Complexes

Angewandte Chemie International Edition  by Tsai-Te Lu, Tsu-Chien Weng, Wen-Feng Liaw  /   14d   //   keep unread   //   hide   //   preview Abstract Extensive study of the electronic structure of Fe-NO complexes using a variety of spectroscopic methods was attempted to understand how iron controls the binding and release of nitric oxide. The comparable energy levels of NO π* orbitals and Fe 3d orbitals complicate the bonding interaction within FeNO complexes and puzzle the quantitative assignment of NO oxidation state. Enemark–Feltham notation, {Fe(NO) x } n , was devised to circumvent this puzzle. This 40-year puzzle is revisited using valence-to-core X-ray emission spectroscopy (V2C XES) in combination with computational study. DFT calculation establishes a linear relationship between ΔE σ2s*-σ2p  of NO and its oxidation state. V2C Fe XES study of FeNO complexes reveals the ΔE σ2s*-σ2p ...

Acidity and Hydrogen Exchange Dynamics of Iron(II)-Bound Nitroxyl in Aqueous Solution

Angewandte Chemie International Edition  by Yin Gao, Abouzar Toubaei, Xianqi Kong, Gang Wu  /   14d   //  keep unread   //   hide   //   preview Abstract Nitroxyl-iron(II) (HNO-Fe II ) complexes are often unstable in aqueous solution, thus making them very difficult to study. Consequently, many fundamental chemical properties of Fe II -bound HNO have remained unknown. Using a comprehensive multinuclear ( 1 H,  15 N,  17 O) NMR approach, the acidity of the Fe II -bound HNO in [Fe(CN) 5 (HNO)] 3−  was investigated and its p K a  value was determined to be greater than 11. Additionally, HNO undergoes rapid hydrogen exchange with water in aqueous solution and this exchange process is catalyzed by both acid and base. The hydrogen exchange dynamics for the Fe II -bound HNO have been characterized and the obtained benchmark values, when combined with the literature data on proteins, reveal ...

Homogeneous Electrocatalytic Water Oxidation at Neutral pH by a Robust Macrocyclic Nickel(II) Complex

ニッケルオキシルラジカルをていしょうしています。 Angewandte Chemie International Edition  by Mei Zhang, Ming-Tian Zhang, Cheng Hou, Zhuo-Feng Ke, Tong-Bu Lu  /   14d   //   keep unread   //   hide   //   preview Abstract The development of an earth-abundant, first-row water oxidation catalyst that operates at neutral pH and low overpotential remains a fundamental chemical challenge. Herein, we report the first nickel-based robust homogeneous water oxidation catalyst, which can electrocatalyze water oxidation at neutral pH and low overpotential in phosphate buffer. The results of DFT calculations verify that the OO bond formation in catalytic water oxidation prefers a HOOH coupling mechanism from a  cis -isomer of the catalyst. The first nickel-based  homogeneous water oxidation catalyst has been reported, which can efficiently electrocatalyze water oxidation at neutral pH in phosphate buffer. The  cis ...

Non-heme iron hydroperoxo species in superoxide reductase as a catalyst for oxidation reactions

Stephanie Rat ,   Stephane Menage ,   Fabrice Thomas  and   Vincent Niviere    ...

Isolation of a (Dinitrogen)Tricopper(I) Complex

Leslie J. Murray   * † ,  Walter W. Weare   ‡ ,  Jason Shearer   § ,  Alyssa D. Mitchell   † , and  Khalil A. Abboud † †  Department of Chemistry, Center for Catalysis, University of Florida , Gainesville, Florida 32611,  United States ‡  Department of Chemistry,  North Carolina State University , Raleigh, North Carolina 27695,  United States §  Department of Chemistry,  University of Nevada , Reno, Reno, Nevada 89557,  United States J. Am. Chem. Soc. , Article ASAP DOI:  10.1021/ja506445d Publication Date (Web): September 19, 2014 Copyright © 2014 American Chemical Society murray@chem.ufl.edu Abstract Reaction of a tris(β-diketimine) cyclophane, H 3 L , with benzyl potassium followed by [Cu(OTf)] 2 (C 6 H 6 ) affords a tricopper(I) complex containing a bridging dinitrogen ligand. rRaman (ν N–N  = 1952 cm –1 ) and  15 N NMR (δ = 303.8 ppm) spectroscopy confirm ...

A chameleon catalyst for nonheme iron-promoted olefin oxidation

Shyam Iyer ,     Maedeh M. Javadi ,     Yan Feng ,     Min Young Hyun ,   Williamson N. Oloo ,     Cheal Kim  and     Lawrence Que Jr.    Chem. Commun. , 2014, Accepted Manuscript DOI:  10.1039/C4CC06164K Accepted 17 Sep 2014 First published online 17 Sep 2014 | | Share on citeulike | Share on facebook | Share on twitter | | More PDF Rich HTML    Send PDF to Kindle Download Citation BibTex   EndNote   MEDLINE   ProCite   ReferenceManager   RefWorks   RIS   Request Permissions Abstract Cited by Related Content   We report the chameleonic reactivity of two nonheme iron catalysts for olefin oxidation with H2O2. In the absence of acetic acid, the catalysts favor the cis-dihydroxylation of electron-poor olefins, but exclusively epoxidize electron-rich olefins upon ...