Itoh Group Literature Review

Chem. Eur. J. 10.1002/chem.201902812 http://dx.doi.org/10.1002/chem.201902812 Authors: Giuseppe Spedalotto, Robert Gericke, Marta Lovisari, Erik Farquhar, Brendan Twamley, and Aidan Richard McDonald ヒドロキソ架橋の高原子価二核錯体は酵素の活性種に多く見られることから注目されている。本論文では上図のNi(II)Ni(II)ヒドロキソ錯体（１）にCANを添加することにより、ヒドロキソ架橋構造を変えずに Ni(II)Ni(III)錯体（２）、さらに Ni(III)Ni(III)錯体（３）へと酸化反応が進行することを初めて見出した。 これらの錯体の生成はEPR、UV-vis spectroscopy、XANES、DFT計算により支持されている。 また、錯体2および3に関しては、各種bis(μ-oxo)錯体と反応性の比較が行われており、錯体3が高い反応性を示すことが明らかとなった。

Reductive O2 Binding at a Dihydride Complex Leading to Redox Interconvertible μ‑1,2-Peroxo and μ‑1,2-Superoxo Dinickel(II) Intermediates J. Am. Chem. Soc. 2018, 140, 4929−4939 DOI: 10.1021/jacs.8b01468 今回の新規な配位子の合成方法は以下のようになります。 J. Am. Chem. Soc. 2017, 139, 16720−16731 DOI: 10.1021/jacs.7b08629

Peng-Cheng Duan,† Dennis-Helmut Manz,† Sebastian Dechert,† Serhiy Demeshko,† and Franc Meyer*,†,‡ †Institut für Anorganische Chemie and ‡International Center for Advanced Studies of Energy Conversion (ICASEC), Universität Göttingen, Tammannstr. 4, D-37077 Göttingen, Germany DOI: 10.1021/jacs.8b01468 I will introduce this paper at next journal meeting. This paper report the smooth reductive O2 binding in the cleft of a dinickel(II) core via elimination of H2 from the corresponding dinickel(II) dihydride complex. This was  the first μ-1,2-peroxo dinickel intermediates to be characterized by X-ray diffraction. This work provides an entire new series of closely related and comprehensively characterized (including elemental analyses) Ni2/O2 intermediates, viz. the mutually interconvertible μ-1,2-superoxo and μ-1,2-peroxo species as well as the K+ adduct of the latter, all based on the same pyrazolate-based {LNi2} scaffold.

Sudipta Pal‡, You-Yun Zhou‡, and Christopher Uyeda* Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States J. Am. Chem. Soc., Article ASAP DOI: 10.1021/jacs.7b05901 Publication Date (Web): August 14, 2017 Copyright © 2017 American Chemical Society http://pubs.acs.org/doi/10.1021/jacs.7b05901 1,1-ジクロロアルケンをカルベンソースとして用いてシクロプロパン化を行う論文です。 中身はともかく、錯体がかっこいいですね。

Eugene Chong,† Jeff W. Kampf,† Alireza Ariafard,*,‡ Allan J. Canty,*,‡ and Melanie S. Sanford*,† †Department of Chemistry, University of Michigan, 930 N. University Avenue, Ann Arbor, Michigan 48109, United States ‡School of Physical Sciences, University of Tasmania, Hobart, Tasmania 7001, Australia J.Am. Chem.Soc . 2017 , 139 , 6058-6061 DOI: 10.1021/jacs.7b02387 [質問] -F　と　-CF 3 　の置換基の違いでニッケル４価錯体の収率が変わってくるのはなぜか。 [回答] 　 　ハロゲンは強い電子求引生誘起効果が弱い電子供与性共鳴効果に打ち勝つため、不活性化基ですが、弱いとはいえハロゲンの非共有電子対の電子供与により、オルト位とパラ位での反応で生じるカルボカチオン中間体を安定化することができます。しかし、トリフルオロ基は共鳴構造において、正に分極したトリフルオロ基の炭素原子と正電荷が反発的な相互作用をするため、オルトとパラ中間体の共鳴構造を不安定化させるので、メタ配向性となります。よって、ハロゲン置換基に比べてトリフルオロ基は、上図の反応において著しく収率を下げたと考えられます。

Dachao Hong†‡ , Yuto Tsukakoshi†, Hiroaki Kotani† , Tomoya Ishizuka†, and Takahiko Kojima*†  †  Department of Chemistry, Faculty of Pure and Applied Sciences,  University of Tsukuba and CREST (JST) , 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571,  Japan ‡  Interdisciplinary Research Center for Catalytic Chemistry,  National Institute of Advanced Industrial Science and Technology (AIST) , Tsukuba, Ibaraki 305-8565,  Japan J. Am. Chem. Soc. , Article ASAP DOI:  10.1021/jacs.7b01956 Publication Date (Web): April 28, 2017 Copyright © 2017 American Chemical Society この論文では、S2N2タイプの配位子を有するニッケル錯体を用いて、二酸化炭素を一酸化炭素に還元する効率的な光触媒反応系について報告しています。 この触媒反応系では、光増感剤として[Ru(bpy)3]2+を、電子供与体してBIHを用いています。 太陽エネルギーによって、二酸化炭素を一酸化炭素やギ酸、メタノールに変換することは、環境エネルギー問題を解決するため重要な反応として注目されています。 このニッケル錯体を用いることで、これまで報告されてきたCO2還元ニッケル錯体と比較して ①高い触媒回転数、②高いCO選択性、③高い量子収率 を達成しました。 S原子がニッケル中心に配位することで、上のスキームに示す反応活性種である低原子価のニッケル中間体（[Ni0L]0）が安定化されるため、この錯体は効率の...

Wen Zhou † ,  Shuai Zheng † ,  Jason W. Schultz † ,  Nigam P. Rath ‡ , and  Liviu M. Mirica * † †  Department of Chemistry,  Washington University , St. Louis, Missouri 63130-4899,  United States ‡  Department of Chemistry and Biochemistry,  University of Missouri—St. Louis , St. Louis, Missouri 63121-4400,  United States J. Am. Chem. Soc. ,  2016 ,  138  (18), pp 5777–5780 DOI:  10.1021/jacs.6b02405 Publication Date (Web): April 27, 2016 Copyright © 2016 American Chemical Society http://pubs.acs.org/doi/abs/10.1021/jacs.6b02405 Abstract Herein we report an atom- and step-economic aromatic cyanoalkylation reaction that employs nitriles as building blocks and proceeds through C sp 2 –H and C sp 3 –H bond activation steps mediated by Ni III . In addition to cyanomethylation with MeCN, regioselective α-cyanoalkylation was observed with various nitrile substrates to generate secondary and tertia...

Communication Quercetin 2,4-Dioxygenase Activates Dioxygen in a Side-On O 2 –Ni Complex Authors Dr. Jae-Hun Jeoung, Dr. Dimitrios Nianios, Prof. Dr. Susanne Fetzner, Prof. Dr. Holger Dobbek Humboldt-University, Berlin   First published:  5 February 2016 Full publication history DOI:  10.1002/anie.201510741 View/save citation Cited by:  0  articles  Check for new citations Funding Information http://onlinelibrary.wiley.com/doi/10.1002/anie.201510741/epdf Abstract Quercetin 2,4-dioxygenase (quercetinase) from  Streptomyces  uses nickel as the active-site cofactor to catalyze oxidative cleavage of the flavonol quercetin. How this unusual active-site metal supports catalysis and O 2  activation is under debate. We present crystal structures of Ni-quercetinase in three different states, thus providing direct insight into how quercetin and O 2  are activa...

Alexander Jeremies † ,  Sina Gruschinski † ,  Michel Meyer * ‡ ,  Vitaly Matulis § ,  Oleg A. Ivashkevich ∥ ,  Karolin Kobalz † , and  Berthold Kersting * † †  Institut für Anorganische Chemie,  Universität Leipzig , Johannisallee 29, 04103 Leipzig,  Germany ‡  Institut de Chimie Moléculaire de l’Université de Bourgogne (ICMUB), UMR 6302, CNRS,  Université de Bourgogne-Franche Comté , 9 avenue Alain Savary, BP 47870, 21078 Dijon Cedex,  France §  Research Institute for Physical Chemical Problems of Belarusian State University, Leningradskaya 14, 220030 Minsk, Belarus ∥   Belarusian State University , 4 Nezavisimisti Avenue, 220050 Minsk,  Belarus Inorg. Chem. , Article ASAP DOI:  10.1021/acs.inorgchem.5b02743 Publication Date (Web): February 2, 2016 Copyright © 2016 American Chemical Society *E-mail:  michel.meyer@u-bourgogne.fr . Fax:  +33/(0)3 80 39 61 17 ., *E-mail:  b...

Journal of the American Chemical Society by W. Curtis Anderson, Jennifer L. Rhinehart, Andrew G. Tennyson and Brian K. Long  /  7d  //  keep unread  //  hide  //  preview http://pubs.acs.org/doi/10.1021/jacs.5b12322   http://pubs.acs.org/doi/pdf/10.1021/jacs.5b12322     Journal of the American Chemical Society DOI: 10.1021/jacs.5b12322 Visit Website

Journal of the American Chemical Society by Daiki Shimizu, Juwon Oh, Ko Furukawa, Dongho Kim and Atsuhiro Osuka  / Journal of the American Chemical Society DOI: 10.1021/jacs.5b11223 abstract 5-Hydroxy-10,15,20-triarylporphyrin (oxophlorin) and its Ni(II) and Zn(II) complexes were oxidized with PbO 2 to give the corresponding porphyrin meso -oxy radicals as remarkably stable species. These radicals were fully characterized with X-ray diffraction analysis, UV/vis/NIR absorption and ESR spectroscopies, magnetic susceptibility measurement, electrochemical studies, and theoretical calculations. Free-base radical and its Ni(II) complex have been shown to exist as a monoradical in solution, while the Zn(II) complex exists in an equilibrium between monomer (doublet monoradical) and dimer (a non-Kekulé singlet biradicaloid) with a dimerization constant of K D = 3.0 × 10 5 M –1 in noncoordinating CH 2 Cl 2 but becomes a pyridine-coordinated monoradical upon a...