雑誌会回答(20191023)

雑誌会回答(20191023)_安

Preparation and characterisation of a bis-μ-hydroxo-Ni(III)2 complex

Giuseppe Spedalotto, Robert Gericke, Marta Lovisari, Erik R. Farquhar, Brendan Twamley, Aidan R. McDonald

DOI: 10.1002/chem.201902812

Chem. Eur. J. 2019, 25, 11983-11990.

This paper shows the synthesis, characterization, and reactivity properties of bis-μ-hydroxo-Ni(II)Ni(III) and bis-μ-hydroxo-Ni(III)2 complexes. It is a first example of high-valent bis-μ-hydroxo-Ni2 complexes.

Q1; [Ni(DMSO)6](ClO4)2 はどこで手に入れた？

A1; 本論文中ではこのNi塩ついての合成や購入の有無についての記載はありませんでした。

僕が調べた限りではこのNi塩は売られていませんでした。合成方法に関しては、試薬会社から入手可能なNi塩である[Ni(H2O)6](ClO4)2 をDMSOに溶かし、数時間加熱し、その後冷やすことで [Ni(DMSO)6](ClO4)2の結晶が得られるようです。

Elzbieta Szostak and co-workers, Journal of Physical Sciences, Volume 62, Issue 1-2, Pages 67-74.

DOI; https://doi.org/10.1515/zna-2007-1-210

Q2; Complex 1と2の立体構造の違いについて

A2; Complex 1に関しては結晶構造のτ値が0.22であったことから歪んだsquare-planar構造であることがわかっています。

また、Complex 1と2のEXAFS測定の結果は以下のようになり、

これらの値はDFT計算の結果より、いずれも歪んだsquare-planar構造であるseesaw型であることがわかりました。よって、Complex1と2で立体構造は変化していません。

Q3; hydroxo架橋のhydroxo anionはどこからくるのか。

A3; 著者らは反応に用いたDMF溶媒に含まれる水の存在が重要だと述べています。

しかし、Complex 1は系中に水が多すぎると不安定ることも述べられていました。

Q4; DFT計算で中心Niの酸化数がわかるか

A4; Mulliken spin density plot測定が行われています。Complex 3に関しては、dz2 characterにNi(III)中心は(triplet: 0.909, 0.918; singlet; 0.900, -0.912)の電子スピン密度あることが計算によりわかっています。S=1およびS=0の状態のいずれも安定であり、0.12 kcal/molしかエネルギー差はありませんでした。

Electrochemical evidence that pyranopterin redox chemistry controls the catalysis of YedY, a mononuclear Mo enzyme

Hope Adamson a, Alexandr N. Simonov b, Michelina Kierzek c, Richard A. Rothery c, Joel H. Weiner c, Alan M. Bond b, and Alison Parkin a,1 a Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom; b School of Chemistry, Monash University, Clayton, VIC 3800, Australia; and c Department of Biochemistry, University of Alberta, Edmonton, AB T6G 2H7, Canada Edited by Harry B. Gray, California Institute of Technology, Pasadena, CA, and approved October 13, 2015 (received for review August 25, 2015) http://www.pnas.org/content/112/47/14506.short A long-standing contradiction in the field of mononuclear Mo enzyme research is that small-molecule chemistry on active-site mimic compounds predicts ligand participation in the electron transfer reactions, but biochemical measurements only suggest metal-centered catalytic electron transfer.With the simultaneous measurement of substrate turnover and reversible electron transfer that is provided by Fourier-...

Tuning Reactivity and Selectivity in Hydrogen Atom Transfer from Aliphatic C–H Bonds to Alkoxyl Radicals: Role of Structural and Medium Effects

Michela Salamone and Massimo Bietti* Dipartimento di Scienze e Tecnologie Chimiche, Università “Tor Vergata”, Via della Ricerca Scientifica, Italy Acc. Chem. Res., Article ASAP DOI: 10.1021/acs.accounts.5b00348 Publication Date (Web): November 6, 2015 クメンパーオキシドを光で開裂させることにより、生成するクミルアルコキシルラジカルによるアルカンやアミンのC–H切断の速度定数などの情報がまとまっています。溶媒や、酸、基質の形が反応速度定数に与える影響を定量的に評価しています。酸化反応をしている方は、手元に置いておいても良いのでしょうか。

Rhenium(V)–oxo corrolazines: isolating redox-active ligand reactivity

Jan Paulo T. Zaragoza,a Maxime A. Sieglera and David P. Goldberg* Chem. Commun., 2015, Advance Article DOI: 10.1039/C5CC07956J Received 22 Sep 2015, Accepted 15 Oct 2015 First published online 28 Oct 2015 http://pubs.rsc.org/en/content/articlelanding/2015/cc/c5cc07956j#!divAbstract Abstract The synthesis of the first example of a third-row metallocorrolazine characterized by single crystal X-ray diffraction is reported. This ReV(O) porphyrinoid complex shows an exclusively ligand-based reactivity with strong acids and oxidizing agents. The one-electron oxidized π-radical-cation complex is capable of H-atom abstraction.

C–H Bond Oxidation Catalyzed by an Imine-Based Iron Complex: A Mechanistic Insight

Giorgio Olivo§¶, Martina Nardi§, Diego Vìdal¶, Alessia Barbieri§, Andrea Lapi§‡, Laura Gómez¶⊥, Osvaldo Lanzalunga§‡, Miquel Costas*¶, and Stefano Di Stefano*§‡ § Università degli Studi di Roma, Rome, Italy ¶ Institut de Química Computacional i Catàlisi (IQCC), Girona, Spain Inorg. Chem., 2015, 54 (21), pp 10141–10152 DOI: 10.1021/acs.inorgchem.5b01500 Publication Date (Web): October 12, 2015 A family of imine-based nonheme iron(II) complexes (LX)2Fe(OTf)2 has been prepared, characterized, and employed as C–H oxidation catalysts. Ligands LX (X = 1, 2, 3, and 4) stand for tridentate imine ligands resulting from spontaneous condensation of 2-pycolyl-amine and 4-substituted-2-picolyl aldehydes. Fast and quantitative formation of the complex occurs just upon mixing aldehyde, amine, and Fe(OTf)2 in a 2:2:1 ratio in acetonitrile solution. The solid-state structures of (L1)2Fe(OTf)(ClO4) and (L3)2Fe(OTf)2 are reported, showing a low-spin octahedral iron center, with the lig...

Oxidative Alkene Cleavage Catalysed by Manganese-Dependent Cupin TM1459 from Thermotoga maritima

van Hajnal 1 , Kurt Faber 1,2 , Helmut Schwab 1,3 , Mélanie Hall 2,* and Kerstin Steiner 1,* a acib, Austrian Centre of Industrial Biotechnology GmbH, Petersgasse 14, 8010 Graz, Austria Fax: ( + 43)-316-873-9302; phone: ( + 43)-316-873-9346; e-mail: kerstin.steiner@acib.at b Department of Chemistry, University of Graz, Heinrichstraße 28, 8010 Graz, Austria Fax: ( + 43)-316-380-9840; phone: ( + 43)-316-380-5479; e-mail: melanie.hall@uni-graz.at c Institute of Molecular Biotechnology, TU Graz, Petersgasse 14, 8010 Graz, Austria Adv .S ynth. Catal. 2015 , 357 , 3 309 –3 316 DOI: 10.1002/adsc.201500608 Abstract A novel biocatalytic oxidative alkene cleavage activity was identified in protein TM1459 from Thermotoga maritima , a so far uncharacterised metalloprotein with a cupin fold, which preferentially binds manganese (over iron and zinc). Various styrene derivat...

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