Itoh Group Literature Review

Dmytro S.NesterovOksana V.NesterovaArmando J.L.Pombeiro Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal Received 17 June 2017, Revised 6 August 2017, Accepted 12 August 2017, Available online 1 September 2017. https://doi.org/10.1016/j.ccr.2017.08.009 Coord Chem Rev 2018 2018年でちょっと古いですが、二核のFirst Law Transition Metal を触媒、過酸化水素を酸化剤として、アルカンを酸化した仕事をまとめた総説です。 メタンの酸化についても情報があります。 中西さんがやっていた、三角なんかも乗っています。

Nichole A. Schwartz, Nicholas C. Boaz, Steven E. Kalman, Thompson Zhuang, Jonathan M. Goldberg, Ross Fu, Robert J. Nielsen, William A. Goddard, John T. Groves,* T. Brent Gunnoe* Cite This:ACS Catal.2018843138-3149 Publication Date:March 13, 2018 https://doi.org/10.1021/acscatal.7b04397 Copyright © 2018 American Chemical Society Comp I でおなじみ、Groves Groupと、ACS Catのアソシエイトエディター Gunnoe のグループの共同研究です。 過ヨウ素酸を酸化剤として、メタンを酸化しています。 トリフルオロメタン中で反応を行うことで、酸化されたメタンはトリフルオロ酢酸メチルエステルへと変換され、懸念される過剰酸化が起こりません。 添加物として、KClとI2を入れるところがミソであり、クロロラジカルが活性種だとされています。クロロメタンも生成します。やっぱり、クロロラジカルは強い。 ヨウ素は生成したメチルラジカルを補足するとされており、生成したヨードメタンがトリフルオロ酢酸と反応するようです。 添付のスキームにあるIO2·は、ヨウ素酸から生成するようです。 Gunnou グループのHPを見ると、いい感じの二核錯体が並んでいます。二核に興味がある人は、フォローしたほうがいいかも。 https://gunnoelab.virginia.edu/first-row-transition-metal-catalysts-selective-hydrocarbon-oxidation

Yan Fang Liu *   The Key Laboratory of Biobased Materials, The Qingdao Key Lab of Solar Energy Utilization and Energy Storage Technology, Qingdao Institute of Bioenergy and Bioprocess Technology ,  Chinese Academy of Sciences ,  Qingdao ,  Shandong   266101 ,  People’s Republic of China Likai Du *   Hubei Key Laboratory of Agricultural Bioinformatics, College of Informatics ,  Huazhong Agricultural University ,  Wuhan ,  430070 ,  People’s Republic of China The reactivity patterns of a series of trivalent copper complexes have been studied to gain a better understanding of the chemical reactions occurring at the active site of particulate methane monooxygenase (pMMO). In this study, hybrid density functional theory is used to study the oxidation of methane to methanol mediated by the [Cu II Cu II (μ-O) 2 Cu III (7- N -Etppz)] 1+  complex. Reaction mechanisms in different spin states were explored. Based ...

Lili Cao, Octav Caldararu, Amy C. Rosenzweig, and Ulf Ryde* Abstract: Particulate methane monooxygenase (pMMO) is one of the few enzymes that can activate methane. The metal content of this enzyme has been highly controversial, with suggestions of a dinuclear Fe site or mono-, di-, or trinuclear Cu sites. Crystal structures have shown a mono- or dinuclear Cu site, but the resolution was low and the geometry of the dinuclear site unusual. We have employed quantum refinement (crystallographic refinement enhanced with quantum-mechanical calculations) to improve the structure of the active site. We compared a number of different mono- and dinuclear geometries, in some cases enhanced with more protein ligands or one or two water molecules, to determine which structure fits two sets of crystallographic raw data best. In all cases, the best results were obtained with mononuclear Cu sites, occasionally with an extra water molecule. Thus, we conclude that there is no crystallographic support ...

Yuta Hori,† Yoshihito Shiota,*,† Tomokazu Tsuji,‡ Masahito Kodera,‡ and Kazunari Yoshizawa*,† † Institute for Materials Chemistry and Engineering and IRCCS, Kyushu University, Fukuoka 819-0395, Japan ‡ Department of Molecular Chemistry and Biochemistry, Doshisha University, Kyotanabe, Kyoto 610-0321, Japan http://pubs.acs.org/doi/10.1021/acs.inorgchem.7b02563 DOI: 10.1021/acs.inorgchem.7b02563 Inorg. Chem. 2018, 57, 8−11 小寺先生と吉澤先生の論文です。 ベンゼンの水酸化で用いた銅の二核錯体を基に、DFT計算からメタンの酸化について検討されています。