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2014の投稿を表示しています

A Ferromagnetically Coupled (S=1) Peroxodicopper(II) Complex

Angewandte Chemie Interna...  by Nicole Kindermann, Eckhard Bill, Sebastian Dechert, Serhiy Demeshko, Edward J. Reijerse, Franc Meyer  /  5d  //  keep unread  //  hide  //  preview Abstract Copper enzymes play important roles in the binding and activation of dioxygen in biological systems. Key copper/dioxygen intermediates have been identified and studied in synthetic analogues of the metalloprotein active sites, including the μ-η 2 :η 2 -peroxodicopper(II) motif relevant to type III dicopper proteins. Herein, we report the synthesis and characterization of a bioinspired dicopper system that forms a stable μ-η 1 :η 1 -peroxo complex whose Cu-O-O-Cu torsion is constrained to around 90° by ligand design. This results in sizeable ferromagnetic coupling between the copper(II) ions, which is detected by magnetic measurements and HF-EPR spectroscopy. The new dicopper peroxo system is the first wit...

Synthesis of Bis(imidazole) Metal Complexes and Their Use in Rapid NO Detection and Quantification Devices

ACS ActiveView PDF Hi-Res Print, Annotate, Reference QuickView PDF  [5138 KB] PDF w/ Links [636 KB] Full Text HTML Abstract Supporting Info -> Figures Reference QuickView Add to ACS ChemWorx Eric Victor   ,  Sunghee Kim   , and  Stephen J. Lippard   * Department of Chemistry,  Massachusetts Institute of Technology , Cambridge, Massachusetts 02139,  United States Inorg. Chem. ,  2014 ,  53  (24), pp 12809–12821 DOI:  10.1021/ic501765g Publication Date (Web): November 24, 2014 Copyright © 2014 American Chemical Society *E-mail:  lippard@mit.edu . Phone:  (617) 253-1892 . Fax:  (617) 258-8150 . Synopsis A series of colorimetric sensors were developed with the motif M(BIPhMe)X2. The reactivity of these complexes toward NO(g) and NO2(g) in solution was explored and characterized. These complexes were then incorporated into test strips and syringes to provide devices that c...

Efficient photochemical water oxidation by a dinuclear molecular ruthenium complex

Chem. Commun. , 2015, Advance Article DOI : 10.1039/C4CC08606F, Communication Tanja M. Laine, Markus D. Karkas, Rong-Zhen Liao, Torbjorn Akermark, Bao-Lin Lee, Erik A. Karlsson, Per E. M. Siegbahn, Bjorn Akermark A dinuclear Ru complex housing an anionic ligand scaffold has been developed. The designed Ru complex was found to efficiently mediate the photochemical oxidation of H 2 O when using [Ru(bpy) 3 ] 2+ -type photosensitizers. To cite this article before page numbers are assigned, use the DOI form of citation above. The content of this RSS Feed (c) The Royal Society of Chemistry

Non-redox metal ion promoted oxygen transfer by a non-heme manganese catalyst

RSC - Chem. Commun. latest articles  by Zhuqi Chen  /   2d   //   keep unread   //   hide   //   preview Chem. Commun. , 2015, Advance Article DOI : 10.1039/C4CC07981G, Communication Zhuqi Chen, Ling Yang, Cholho Choe, Zhanao Lv, Guochuan Yin Non-redox metal ions can help the dissociation of the dinuclear Mn 2 ( III , IV ) core, leading to sharp improvement in its oxygen transfer efficiency. To cite this article before page numbers are assigned, use the DOI form of citation above. The content of this RSS Feed (c) The Royal Society of Chemistry Visit Website

Reduction of ​carbon dioxide to ​oxalate by a binuclear copper complex

Uttam R. Pokharel , Frank R. Fronczek &  Andrew W. Maverick Affiliations Contributions Corresponding author Nature Communications   5 ,   Article number:   5883   doi:10.1038/ncomms6883 Received   01 June 2014  Accepted   18 November 2014  Published   19 December 2014 Article tools PDF Citation Reprints Rights & permissions Article metrics Abstract Abstract •   Introduction •   Results •   Discussion •   Methods •   Additional information •   References • Acknowledgements •   Author information •   Supplementary information Reduction of ​ carbon dioxide  to products such as ​ oxalate  (​ C 2 O 4 2− ) is an active area of research, as the process converts an environmental pollutant into more useful organic compounds. However, ​ carbon dioxide  reduction remains a major challenge. Here we demonstrate a three-step reaction ...

Reduction of carbon dioxide to oxalate by a binuclear copper complex

Nature Communications  by Uttam R. Pokharel  /   3h   //   keep unread   //   hide   //   preview Article Although value-added organics are traditionally synthesized from fossil feedstocks, the conversion of carbon dioxide is an attractive alternative route. Here, the authors report a cyclic copper complex capable of converting carbon dioxide to oxalate in a simple redox process under mild conditions. Nature Communications  doi: 10.1038/ncomms6883 Authors: Uttam R. Pokharel, Frank R. Fronczek, Andrew W. Maverick Visit Website

Networked-Cage Microcrystals for Evaluation of Host–Guest Interactions

ACS ActiveView PDF Hi-Res Print, Annotate, Reference QuickView PDF  [1300 KB] PDF w/ Links [246 KB] Full Text HTML Abstract Supporting Info -> Figures Reference QuickView Add to ACS ChemWorx Shohei Matsuzaki   ,  Tatsuhiko Arai   ,  Koki Ikemoto   ,  Yasuhide Inokuma   , and  Makoto Fujita   * Department of Applied Chemistry, School of Engineering,  The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656,  Japan J. Am. Chem. Soc. , Article ASAP DOI:  10.1021/ja5109535 Publication Date (Web): December 12, 2014 Copyright © 2014 American Chemical Society mfujita@appchem.t.u-tokyo.ac.jp Abstract We have developed a new synthetic protocol for the preparation of a microcrystalline powder (median size:  X 50  = 25 μm) of networked M 6 L 4  cages  1a  for the stationary phase of an affinity column on a greater than 50 g scale. Analogously to large...

Metal-Free σ-Bond Metathesis in Ammonia Activation by a Diazadiphosphapentalene

ACS ActiveView PDF Hi-Res Print, Annotate, Reference QuickView PDF  [1756 KB] PDF w/ Links [334 KB] Full Text HTML Abstract Supporting Info -> Figures Reference QuickView Add to ACS ChemWorx Jingjing Cui   † ,  Yongxin Li   ‡ ,  Rakesh Ganguly   ‡ ,  Anusiya Inthirarajah   § ,  Hajime Hirao   * † , and  Rei Kinjo   * † †  Division of Chemistry & Biological Chemistry, School of Physical & Mathematical Sciences, and  ‡ NTU-CBC Crystallography Facility,  Nanyang Technological University , Singapore 637371,  Singapore §  School of Chemistry,  University of Edinburgh , Edinburgh EH9 3JJ,  U.K. J. Am. Chem. Soc. ,  2014 ,  136  (48), pp 16764–16767 DOI:  10.1021/ja509963m Publication Date (Web): November 12, 2014 Copyright © 2014 American Chemical Society * rkinjo@ntu.edu.sg , * hirao@ntu.edu.sg Section: Physical Organic Ch...

Crystallographic and spectroscopic characterization and reactivities of a mononuclear non-haem iron(III)-superoxo complex

Non-haem iron superoxo species—proposed as key intermediates in catalytic activation of molecular oxygen—have proven difficult to structurally characterize. Here, the authors obtain crystallographic and spectral characterization of a non-haem iron(III)-superoxo species and subsequently study its reactivity. Nature Communications  doi: 10.1038/ncomms6440 Authors: Seungwoo Hong, Kyle D. Sutherlin, Jiyoung Park, Eunji Kwon, Maxime A. Siegler, Edward I. Solomon, Wonwoo Nam Visit Website

Latent and active abPPO4 mushroom tyrosinase cocrystallized with hexatungstotellurate(VI) in a single crystal

Stephan Gerhard Mauracher, Christian Molitor, Rami Al-Oweini, Ulrich Kortz and Annette Rompel DOI: 10.1107/S1399004714013777  Issue Acta Crystallographica Section D Acta Crystallographica Section D Volume 70, Issue 9, pages 2301–2315, September 2014  Keywords: abPPO4;tyrosinase;polyphenol oxidase; あまり馴染みのない雑誌ですが、 melB とそっくりのプロ型チロシナーゼの構造です。 結晶格子中に活性型とプロ型が混在しています。 Agaricus bisporus Tyrosinases, bifunctional metalloenzymes, catalyze the oxidation of monophenols and o-diphenols to o-quinones, the precursor compounds of the brown-coloured pigment melanin. In eukaryotic organisms, tyrosinases are expressed as latent zymogens that have to be proteolytically cleaved in order to form highly active enzymes. This activation mechanism, known as the tyrosinase maturation process, has scientific and industrial significance with respect to biochemical and technical applications of the enzyme. Here, not only the first crystal structure of the mushroom tyrosinase abPPO4 is presented i...

Non-redox Metal Ions Promoted Oxygen Transfer by a Non-heme Manganese Catalyst

RSC - Chem. Commun. latest articles by Zhuqi Chen  /  1d  //  keep unread  //  hide  //  preview Chem. Commun. , 2014, Accepted Manuscript DOI : 10.1039/C4CC07981G, Communication Zhuqi Chen, ling yang, Cholho Choe, Zhanao Lv, Guochuan Yin   This work demonstrates that non-redox metal ions as Lewis acid can sharply improve the oxygen transfer efficiency of a manganese(II) catalyst having non-heme ligand. In the absence of Lewis acid, oxidation of manganese(II) complex will generate the known di-μ-oxo-bridged dinuclear Mn2(III,IV) core which is very sluggish for olefin epoxidation. Adding non-redox metal ions causes the dissociation of the dinuclear core, leading to sharply improve its oxygen transfer efficiency.  

Formazanate Ligands as Structurally Versatile, Redox-Active Analogues of β-Diketiminates in Zinc Chemistry

Mu-Chieh Chang, Peter Roewen, Raquel Travieso-Puente, Martin Lutz, and Edwin Otten Inorg. Chem. ,  Articles ASAP (As Soon As Publishable) Publication Date (Web):  December 10, 2014  ( Article ) DOI:  10.1021/ic5025873 A range of tetrahedral bis(formazanate)zinc complexes with different steric and electronic properties of the formazanate ligands were synthesized. The solid-state structures for several of these were determined by X-ray crystallography, which showed that ... A series of bis(formazanate)zinc complexes were prepared and characterized both in solution and in the solid state. The redox-active nature of the formazanate ligands was studied by cyclic voltammetry. The impact of the ligand substitution pattern on the structures, redox potentials, and optical properties was established.

The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations

RSC - Chem. Sci. latest articles  by William M. Hart-Cooper  /   5d   //   keep unread   //   hide   //   preview Chem. Sci. , 2015, Advance Article DOI : 10.1039/C4SC02735C, Edge Article Open Access &nbsp This article is licensed under a  Creative Commons Attribution 3.0 Unported Licence. William M. Hart-Cooper, Chen Zhao, Rebecca M. Triano, Parastou Yaghoubi, Haxel Lionel Ozores, Kristen N. Burford, F. Dean Toste, Robert G. Bergman, Kenneth N. Raymond Catalyst and substrate modification, product selectivity and kinetic studies comprehensively describe a new class of terpenoid cyclase mimics. To cite this article before page numbers are assigned, use the DOI form of citation above. The content of this RSS Feed (c) The Royal Society of Chemistry Visit Website