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2月, 2015の投稿を表示しています

Lewis Acid-Induced Change from Four- to Two-Electron Reduction of Dioxygen Catalyzed by Copper Complexes Using Scandium Triflate

Journal of the American Chemical Society: Latest Articles (ACS Publications)  by Saya Kakuda, Clarence J. Rolle, Kei Ohkubo, Maxime A. Siegler, Kenneth D. Karlin and Shunichi Fukuzumi  /   1d   //   keep unread   //   hide   //   preview Journal of the American Chemical Society DOI: 10.1021/ja512584r Visit Website

Cerium(IV)-Driven Water Oxidation Catalyzed by a Manganese(V)–Nitrido Complex

Angewandte Chemie International Edition  by Li Ma, Qian Wang, Wai-Lun Man, Hoi-Ki Kwong, Chi-Chiu Ko, Tai-Chu Lau  /   1d   //   keep unread   //   hide   //   preview Abstract The study of manganese complexes as water-oxidation catalysts (WOCs) is of great interest because they can serve as models for the oxygen-evolving complex of photosystem II. In most of the reported Mn-based WOCs, manganese exists in the oxidation states III or IV, and the catalysts generally give low turnovers, especially with one-electron oxidants such as Ce IV . Now, a different class of Mn-based catalysts, namely manganese(V)–nitrido complexes, were explored. The complex [Mn V (N)(CN) 4 ] 2−  turned out to be an active homogeneous WOC using (NH 4 ) 2 [Ce(NO 3 ) 6 ] as the terminal oxidant, with a turnover number of higher than 180 and a maximum turnover frequency of 6 min −1 . The study suggests that active WOCs may be constructed based on the Mn V (N) platform. High turnover : The study of man

Structural Characterization of a Hydroperoxo Nickel Complex and Its Autoxidation: Mechanism of Interconversion between Peroxo, Superoxo, and Hydroperoxo Species

Angewandte Chemie International Edition  by Christoph A. Rettenmeier, Hubert Wadepohl, Lutz H. Gade  /   7d   //   keep unread   //   hide   //   preview Abstract Pincer-stabilized nickel(I) complexes readily react with molecular oxygen to form dinuclear 1,2-μ-peroxo-bridged nickel(II) complexes, which are the major components of a dynamic equilibrium with the corresponding mononuclear superoxo species. The peroxo complexes further react with hydrogen peroxide to give the corresponding nickel(II) hydroperoxides. One of these hitherto elusive species was characterized by X-ray diffraction for the first time [O–O bond length: 1.492(2) Å]. Pincer-stabilized nickel(I) complexes  readily react with molecular oxygen to form dinuclear 1,2-μ-peroxo-bridged nickel(II) complexes, which are the major components of a dynamic equilibrium with the corresponding mononuclear superoxo species. The peroxo complexes further react with hydrogen peroxide to give the corresponding nickel(II)

Isotope effect profiles in the N-demethylation of N,N-dimethylanilines: a key to determine the pKa of nonheme Fe(III)–OH complexes

Alessia Barbieri , a      Martina De Gennaro , a      Stefano Di Stefano , a    Osvaldo Lanzalunga , * a      Andrea Lapi , a      Marco Mazzonna , a    Giorgio Olivo a  and     Barbara Ticconi a    Show Affiliations Chem. Commun. , 2015, Advance Article DOI:  10.1039/C5CC00411J Received 15 Jan 2015, Accepted 16 Feb 2015 First published online 17 Feb 2015 | | 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   N -demethylation of  N , N -dimethylanilines promoted by [(N4Py)Fe IV O] 2+  occurs by an electron transfer–proton transfer (ET–PT) mechanism with a rate determining PT step. From the bell-shaped curve of the KDIE profile it has been estimated that the p K a  of [(N4Py)Fe III –OH] 2+  is 9.7.

Structural Characterization of a Hydroperoxo Nickel Complex and Its Autoxidation: Mechanism of Interconversion between Peroxo, Superoxo, and Hydroperoxo Species

Angewandte Chemie International Edition  by Christoph A. Rettenmeier, Hubert Wadepohl, Lutz H. Gade  /   5d   //   keep unread  //   hide   //   preview Abstract Pincer-stabilized nickel(I) complexes readily react with molecular oxygen to form dinuclear 1,2-μ-peroxo-bridged nickel(II) complexes, which are the major components of a dynamic equilibrium with the corresponding mononuclear superoxo species. The peroxo complexes further react with hydrogen peroxide to give the corresponding nickel(II) hydroperoxides. One of these hitherto elusive species was characterized by X-ray diffraction for the first time [O–O bond length: 1.492(2) Å]. Pincer-stabilized nickel(I) complexes  readily react with molecular oxygen to form dinuclear 1,2-μ-peroxo-bridged nickel(II) complexes, which are the major components of a dynamic equilibrium with the corresponding mononuclear superoxo species. The peroxo complexes further react with hydrogen peroxide to give the corresponding nic

A N3S(thioether)-Ligated CuII-Superoxo with Enhanced Reactivity

カーリン groupです。 Sunghee Kim   † ,  Jung Yoon Lee   † ,  Ryan E. Cowley   ‡ ,  Jake W. Ginsbach   ‡ ,  Maxime A. Siegler   † ,  Edward I. Solomon   * ‡ , and  Kenneth D. Karlin   * † †  Department of Chemistry,  Johns Hopkins University , Baltimore, Maryland 21218,  United States ‡  Department of Chemistry,  Stanford University , Stanford, California 94305,  United States J. Am. Chem. Soc. , Article ASAP DOI:  10.1021/ja511504n Publication Date (Web): February 20, 2015 Copyright © 2015 American Chemical Society * edward.solomon@stanford.edu , * karlin@jhu.edu Abstract Previous efforts to synthesize a cupric superoxide complex possessing a thioether donor have resulted in the formation of an end-on  trans -peroxo-dicopper(II) species, [{(Ligand)Cu II } 2 (μ-1,2-O 2 2– )] 2+ . Redesign/modification of previous N 3 S tetradentate ligands has now allowed for the stabilization of the monomeric, superoxide product possessing a S (thioether)  ligation, [( DMA N

A N3S(thioether)-Ligated CuII-Superoxo with Enhanced Reactivity

Journal of the American C... by Sunghee Kim, Jung Yoon Lee, Ryan E. Cowley, Jake W. Ginsbach, Maxime A. Siegler, Edward I. Solomon and Kenneth D. Karlin  /  7h  //  keep unread  //  hide  //  preview Journal of the American Chemical Society DOI: 10.1021/ja511504n

Resolution of Key Roles for the Distal Pocket Histidine in Cytochrome c Nitrite Reductases

Colin W. J. Lockwood † , Bénédicte Burlat † , Myles R. Cheesman † , Melanie Kern § , Jörg Simon § , Thomas A. Clarke ‡ , David J. Richardson ‡ , and Julea N. Butt * † ‡ † Centre for Molecular and Structural Biochemistry, School of Chemistry and ‡ School of Biological Sciences, University of East Anglia , Norwich Research Park, Norwich, NR4 7TJ, U.K. § Microbial Energy Conversion and Biotechnology, Department of Biology, Technische Universität Darmstadt , Schnittspahnstrasse 10, 64287 Darmstadt, Germany J. Am. Chem. Soc. , Article ASAP DOI: 10.1021/ja512941j Publication Date (Web): February 6, 2015 Copyright © 2015 American Chemical Society j.butt@uea.ac.uk ACS AuthorChoice - This is an open access article published under a Creative Commons Attribution (CC-BY) License , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. Abstract Cytochrome c nitrite reductas

Electron transfer and catalysis with high-valent metal-oxo complexes

Shunichi Fukuzumi    Dalton Trans. , 2015, Accepted Manuscript DOI:  10.1039/C5DT00204D Received 16 Jan 2015, Accepted 10 Feb 2015 First published online 11 Feb 2015 |  | 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 Metrics   High-valent metal-oxo complexes are produced by reductive activation of dioxygen via reduction of metal complexes with reductants and dioxygen. Photoinduced electron transfer from substrates to metal complexes with dioxygen also leads to generation of high-valent metal-oxo complexes that can oxygenate substrates. In such a case metal complexes act as a photocatalyst to oxygenate substrates with dioxygen. High-valent metal-oxo complexes are also produced by proton-coupled electron-transf

Calorimetric Assessment of Fe2+ Binding to α-Ketoglutarate/Taurine Dioxygenase: Ironing Out the Energetics of Metal Coordination by the 2-His-1-Carboxylate Facial Triad

ACS ActiveView PDF Hi-Res Print, Annotate, Reference QuickView PDF  [1677 KB] PDF w/ Links [349 KB] Full Text HTML Abstract Supporting Info -> Figures Reference QuickView Add to ACS ChemWorx Kate L. Henderson   † ,  Tina A. Müller   ‡ ,  Robert P. Hausinger   ‡ , and  Joseph P. Emerson   * † †  Department of Chemistry,  Mississippi State University , Mississippi State, Mississippi 39762,  United States ‡  Department of Microbiology and Molecular Genetics,  Michigan State University , East Lansing, Michigan 48824-4320,  United States Inorg. Chem. , Article ASAP DOI:  10.1021/ic502881q Publication Date (Web): February 10, 2015 Copyright © 2015 American Chemical Society *E-mail:  jemerson@chemistry.msstate.edu . Phone:  662-325-9500 . Fax:  662-325-1618 . Synopsis The thermodynamic profile associated with Fe2+ binding to the 2-His-1-carboxylate facial triad in TauD is given. Section: Enzymes Abstract The thermodynamic properti