Itoh Group Literature Review

Ikuko Araki ,  Kaoru Fukui , and  Hiroshi Fujii *   Department of Chemistry, Graduate School of Humanities and Sciences,  Nara Women’s University , Kitauoyanishi, Nara 630-8506,  Japan Inorg. Chem. ,  2018 ,  57  (4), pp 1685–1688 DOI:  10.1021/acs.inorgchem.7b02661 Publication Date (Web): February 5, 2018 Copyright © 2018 American Chemical Society *E-mail:  fujii@cc.nara-wu.ac.jp . Synopsis A bis-hypochlorite adduct of a manganese(IV) salen complex having a chiral  trans -cyclohexane-1,2-diamine linkage is successfully prepared and characterized by various spectroscopic methods. The manganese(IV) bis-hypochlorite complex is capable of sulfoxidation, epoxidation, chlorination, and hydrogen abstraction reactions. However, the enantioselectivity of this complex is low, which is consistent with the planar conformation of the salen ligand, as suggested by circular dichroism spectroscopy. https://pu...

Electrocatalytic Water Oxidation by a Homogeneous Copper Catalyst Disfavors Single-Site Mechanisms Sara J. Koepke, Kenneth M. Light, Peter E. VanNatta, Keaton M. Wiley, and Matthew T. Kieber-Emmons*  Department of Chemistry, University of Utah, Salt Lake City, Utah 84112-0850, United States J. Am. Chem. Soc., Article ASAP DOI: 10.1021/jacs.7b03278 Publication Date (Web): May 30, 2017 Copyright © 2017 American Chemical Society *matthew.kieber-emmons@utah.edu http://pubs.acs.org/doi/abs/10.1021/jacs.7b03278 本論文では、銅錯体による水の酸化触媒反応において、二核銅錯体 [(L)Cu(II)]2-(μ-OH)2}(OTf)2 (L = Me2TMPA = bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)- amine（上図右上）が反応活性中間体であるということを報告しています。この二核の反応中間体は 分光学的手法や電気化学的手法さらに計算化学的手法により同定されています。 これまでの銅錯体による水の酸化触媒の反応中間体には、同じような水の酸化触媒であるRu錯体やIr錯体のように単核Cu(IV)O/Cu(III)−O• 錯体を反応中間体として経由し反応が進行すると報告されていました。 DFT計算によってこの二核錯体は ・分子間の水の求核攻撃 ・還元によって生成する {[LCu(III)]2-(μ-O)2}2+ がO-O結合生成のためのpath としてエネルギー的に起こりうるということを明らかにしています。 同じ水の酸化反応におい...

Capturing the Role of Explicit Solvent in the Dimerization of Ru V (bda) Water Oxidation Catalysts Shaoqi Zhan, Daniel Mårtensson, Miha Purg, Shina C. L. Kamerlin, and Mårten S. G. Ahlquist* S. Zhan, D. Mårtensson, Dr. M. S. G. Ahlquist Division of Theoretical Chemistry & Biology School of Biotechnology, KTH Royal Institute of Technology 10691 Stockholm (Sweden) DOI: 10.1002/anie.201701488 Angew. Chem. Int. Ed. 2017 , 56 , 1 – 5   水の酸化の有効な触媒として7配位のRu錯体がある。この錯体はRu(V)=Oを形成したのちdimerとなって水の酸化を行うことが知られている。 本論文は初めてempirical valence bond (EVB)というシュミレーション方法を遷移金属錯体の触媒反応系に用いて、反応系における溶媒の効果を示している。 結論としてはRu=Oオキソの部分が疎水部であることが分かり、疎水性相互作用によりオキソ同士の向きが揃うことが一連の触媒サイクルの足がかりとなっていることを明らかにした。 触媒サイクルにおいての溶媒効果はあいかさんの修士論文で議論されていましたが、こういったシュミレーション方法を実験データを組み合わせて使えるのかなと思いました。

Nature Chemistry. doi:10.1038/nchem.2503 Authors: Marcus Schulze, Valentin Kunz, Peter D. Frischmann & Frank Würthner   http://www.nature.com/nchem/journal/vaop/ncurrent/full/nchem.2503.html http://www.nature.com/nchem/journal/vaop/ncurrent/pdf/nchem.2503.pdf Designing improved catalysts is predicated on understanding how they work. Now, by positioning three ruthenium centres in a macrocyclic framework, a remarkable acceleration of catalytic water oxidation has been achieved. Detailed mechanistic studies revealed that the catalyst operates through the ‘water nucleophilic attack’ pathway—similar to the natural oxygen-evolving cluster of photosystem II.    

Guillaume Passard , Andrew M. Ullman , Casey N. Brodsky , and Daniel G. Nocera * Department of Chemistry and Chemical Biology, Harvard University , 12 Oxford Street, Cambridge, Massachusetts 02138, United States J. Am. Chem. Soc. , Article ASAP DOI: 10.1021/jacs.5b12828 http://pubs.acs.org/doi/abs/10.1021/jacs.5b12828 http://pubs.acs.org/doi/pdf/10.1021/jacs.5b12828 Abstract The selective four electron, four proton, electrochemical reduction of O 2 to H 2 O in the presence of a strong acid (TFA) is catalyzed at a dicobalt center. The faradaic efficiency of the oxygen reduction reaction (ORR) is furnished from a systematic electrochemical study by using rotating ring disk electrode (RRDE) methods over a wide potential range. We derive a thermodynamic cycle that gives access to the standard potential of O 2 reduction to H 2 O in organic solvents, taking into account the presence of an exogenous proton donor. The difference in ORR selectivity for H 2 O...

W olfgang Sc hçfberger ,* F elix F aschinger , Samir Chattopadhyay , Snehadri Bhakta , Biswajit Mondal , J ohannes A. A. W . Elemans , Stefan Müllegger , Stefano T ebi , Reinhold K och , Florian Klappenberger , Mateusz P aszkiewicz , J ohannes V . Barth , Eva Rauls , Hazem Aldahhak , W olf Gero Schmidt , and Abhishek Dey * International Edition: DOI: 10.1002/anie.201508404  German Edition: DOI: 10.1002/ange.201508404  [*] Prof. Dr. W. Schçfberger, Dipl.-Ing. F. Faschinger Institute of Organic Chemistry, Johannes Kepler University Linz Altenberger Strasse 69, 4040 Linz (Austria) S. Chattopadhyay, S. Bhakta, B. Mondal, Prof. Dr. A. Dey Department of Inorganic Chemistry Indian Association for the Cultivation of Science 2A & 2B Raja SC Mullik Road, Kolkata, 700032 (India) Prof. Dr. J. A. A. W. Elemans Radboud University, Institute for Molecules and Materials Heyendaalseweg 135, 6525 AJ Nijmegen (The Netherlands) Prof. Dr...