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Hydrogen Production from a Methanol–Water Solution Catalyzed by an Anionic Iridium Complex Bearing a Functional Bipyridonate Ligand under Weakly Basic Conditions

Prof. Dr. Ken-ichi Fujita * ,  Dr. Ryoko Kawahara,  Takuya Aikawa and Prof. Dr. Ryohei Yamaguchi * View Full Article with Supporting Information (HTML)   Enhanced Article (HTML)   Get PDF (604K) Keywords: dehydrogenation; homogeneous catalysis; hydrogen; iridium; methanol Abstract An efficient catalytic system for the production of hydrogen from a methanol–water solution has been developed using a new anionic iridium complex bearing a functional bipyridonate ligand as a catalyst. This system can be operated under mild conditions [weakly basic solution (0.046 mol L −1  NaOH) below 100 °C] without the use of an additional organic solvent. Long-term continuous hydrogen production from a methanol–water solution catalyzed by the anionic iridium complex was also achieved. 最大で84%のH2 yield がでる (TON 160)。

Oxygen Evolution Catalyzed by a Mononuclear Ruthenium Complex Bearing Pendant SO3− Groups

分子研の正岡グループのお仕事です。活性点近傍に、酸化剤かつ、水の酸化をアシストすると言われているCe(IV)を捕まえる分子設計です。「アイディアを形にする」分子設計だと思います。 Angewandte Chemie International Edition  by Masaki Yoshida, Mio Kondo, Sena Torii, Ken Sakai, Shigeyuki Masaoka  /   13d   //   keep unread   //   hide   //   preview Abstract Rational molecular design of catalytic systems capable of smooth OO bond formation is critical to the development of efficient catalysts for water oxidation. A new ruthenium complex was developed, which bears pendant SO 3 −  groups in the secondary coordination sphere: [Ru(terpy)(bpyms)(OH 2 )] (terpy=2,2′:6′,2′′-terpyridine, bpyms=2,2′-bipyridine-5,5′-bis(methanesulfonate)). Water oxidation driven by a Ce 4+  oxidant is distinctly accelerated upon introduction of the pendant SO 3 −  groups in comparisons to the parent catalyst, [Ru(terpy)(bpy)(OH 2 )] 2+  (bpy=2,2′-bipyridine). Spectroscopic, electrochemical, an...

Nitrite reduction by copper through ligand-mediated proton and electron transfer

25   RSC - Chem. Sci. latest articles  by Cameron M. Moore  /   28d   //   keep unread   //   hide   //   preview Chem. Sci. , 2015, Advance Article DOI : 10.1039/C5SC00720H, Edge Article Open Access &nbsp This article is licensed under a  Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Cameron M. Moore, Nathaniel K. Szymczak A copper complex featuring a proton-responsive tripodal ligand reduces nitrite  via  a proton/electron transfer process, which parallels copper nitrite reductase. 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

Exploiting Metal–Ligand Bifunctional Reactions in the Design of Iron Asymmetric Hydrogenation Catalysts

リガンドが、ベースとしても働く系だそうです。 Accounts of Chemical Research: Latest Articles (ACS Publications)  by Robert H. Morris  /   15d   //   keep unread   //   hide   //   preview Accounts of Chemical Research DOI: 10.1021/acs.accounts.5b00045 Visit Website

Hydrogen Evolution Catalyzed by Cobalt Diimine–Dioxime Complexes

第二配位圏にある、プロトン輸送サイトが大事だとかなんとか Accounts of Chemical Research: Latest Articles (ACS Publications)  by Nicolas Kaeffer, Murielle Chavarot-Kerlidou and Vincent Artero  /   1d   //   keep unread   //   hide   //   preview Accounts of Chemical Research DOI: 10.1021/acs.accounts.5b00058 Visit Website

Cation-Modulated Reactivity of Iridium Hydride Pincer-Crown Ether Complexes

500+   Journal of the American Chemical Society: Latest Articles (ACS Publications)  by Matthew R. Kita and Alexander J. M. Miller  /   7d   //   keep unread   //   hide   //   preview Journal of the American Chemical Society DOI: 10.1021/ja507324s Visit Website

Pendant Acid–Base Groups in Molecular Catalysts: H-Bond Promoters or Proton Relays? Mechanisms of the Conversion of CO2 to CO by Electrogenerated Iron(0)Porphyrins Bearing Prepositioned Phenol Functionalities

活性中心にプロトンを運ぶような置換基の働き Journal of the American Chemical Society: Latest Articles (ACS Publications)  by Cyrille Costentin, Guillaume Passard, Marc Robert and Jean-Michel Savéant  /   13h   //   keep unread   //   hide   //   preview Journal of the American Chemical Society DOI: 10.1021/ja506193v

Beyond the Active Site: The Impact of the Outer Coordination Sphere on Electrocatalysts for Hydrogen Production and Oxidation

Bojana Ginovska-Pangovska   ,  Arnab Dutta   , Matthew L. Reback   ,  John C. Linehan   , and  Wendy J. Shaw   * Pacific Northwest National Laboratory , Richland, Washington 99354,  United States Acc. Chem. Res. , Article ASAP DOI:  10.1021/ar5001742 Publication Date (Web): June 19, 2014 Copyright © 2014 American Chemical Society Abstract 注目の系。 View:  ACS ActiveView PDF  |  PDF  |  PDF w/ Links  |  Full Text HTML

Isolation of Iron(II) Aqua and Hydroxyl Complexes Featuring a Tripodal H-bond Donor and Acceptor Ligand

Ellen M. Matson   ,  Jeffrey A. Bertke   , and  Alison R. Fout   * School of Chemical Sciences,  University of Illinois at Urbana−Champaign , 600 S. Mathews Avenue Urbana, Illinois 61801,  United States Inorg. Chem. , Article ASAP DOI:  10.1021/ic500102c Publication Date (Web): April 23, 2014 Copyright © 2014 American Chemical Society *E-mail:  fout@illinois.edu . Synopsis A tripodal ligand platform, tris(5-cycloiminopyrrol-2-ylmethyl)amine (H3[N(piCy)3]) is reported. The ability of the ligand to tautomerize to the amino azafulvene H3[N(afaCy)3] upon substrate addition is evident in the isolation of a series of iron(II) complexes. The combined data for the iron complexes establishes that each arm of the tripodal ligand can tautomerize independently, depending on electronic needs of the iron center and substrate coordination. Abstract A tripodal ligand platform, tris(5-cycloiminopyrrol-2-ylmethyl)amine (H 3 [N(pi...

Heterolytic Cleavage of Hydrogen by an Iron Hydrogenase Model: An Fe-H⋅⋅⋅H-N Dihydrogen Bond Characterized by Neutron Diffraction†

Communication You have full text access to this content Dr. Tianbiao Liu 1,* ,  Dr. Xiaoping Wang 2 , Dr. Christina Hoffmann 2 ,  Dr. Daniel L. DuBois 1  and Dr. R. Morris Bullock 1,* Article first published online: 22 APR 2014 DOI: 10.1002/anie.201402090 © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Issue Additional Information (Show All) Abstract Article References Supporting Information Cited By View Full Article with Supporting Information (HTML)   Enhanced Article (HTML)   Get PDF (847K) Keywords: enzyme models; hydrogen; hydrogenases; iron; neutron diffraction Abstract Hydrogenase enzymes in nature use hydrogen as a fuel, but the heterolytic cleavage of H H bonds cannot be readily observed in enzymes. Here we show that an iron complex with pendant amines in the diphosphine ligand cleaves hydrogen heterolytically. The product has a strong Fe-H⋅⋅⋅H-N dihydrogen bond. The structure was determine...

Homogeneous Perdehydrogenation and Perhydrogenation of Fused Bicyclic N-Heterocycles Catalyzed by Iridium Complexes Bearing a Functional Bipyridonate Ligand

ピリジンの水酸基がケトンになって、何がおこるのかは詳細には分かりませんが、たぶんなんかしら重要なんでしょう。 Communication ACS ActiveView PDF Hi-Res Print, Annotate, Reference QuickView PDF  [619 KB] PDF w/ Links [310 KB] Full Text HTML Abstract Supporting Info -> Figures Reference QuickView Add to ACS ChemWorx Ken-ichi Fujita   * ,  Yui Tanaka   ,  Masato Kobayashi   , and  Ryohei Yamaguchi   * Graduate School of Human and Environmental Studies, Kyoto University , Sakyo-ku, Kyoto 606-8501,  Japan J. Am. Chem. Soc. ,  2014 ,  136  (13), pp 4829–4832 DOI:  10.1021/ja5001888 Publication Date (Web): March 24, 2014 Copyright © 2014 American Chemical Society yamaguchi.ryohei.75s@st.kyoto-u.ac.jp , fujita.kenichi.6a@kyoto-u.ac.jp Section: Heterocyclic Compounds (More than One Hetero Atom) Abstract Homogeneous perdehydrogenation of saturated bicyclic 2,6-dimethyldecahydro-1,5-naphthyridine and perhydrogena...