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Generation and Reactivity of a One‐electron Oxidized Manganese(V) Imido Complex bearing a Macrocyclic Tetraamido Ligand

Tai-Chu Lau,  Huatian Shi,  Jianhui Xie,  William W. Y. Lam,  Wai-Lun Man,  Chi-Keung Mak, Shek-Man Yiu,  Hung-Kay Lee Eur. J. Chem 2019 First published: 20 July 2019 https://doi.org/10.1002/chem.201902405 Tai-Chu Lauらのグループから、マンガン(V)-イミド錯体についての報告です。支持配位子は、鉄(V)-オキソ錯体の研究でもよく用いられている、TAML系の配位子です。 彼らは、結晶構造を得ることにも、成功しています。

Dioxygen Activation by a Macrocyclic Copper Complex Leads to a Cu2O2 Core with Unexpected Structure and Reactivity

Abstract We report the Cu I /O 2   chemistry of complexes derived from the macrocylic ligands 14-TMC (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and 12-TMC (1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). While [(14-TMC)Cu I ] +   is unreactive towards dioxygen, the smaller analog [(12-TMC)Cu I (CH 3 CN)] +   reacts with O 2   to give a side-on bound peroxo-dicopper(II) species ( S P), confirmed by spectroscopic and computational methods. Intriguingly, 12-TMC as a N4 donor ligand generates   S P species, thus in contrast with the previous observation that such species are generated by N2 and N3 ligands. In addition, the reactivity of this macrocyclic side-on peroxo-dicopper(II) differs from typical   S P species, because it reacts only with acid to release H 2 O 2 , in contrast with the classic reactivity of Cu 2 O 2   cores. Kinetics and computations are consistent with a protonation mechanism whereby the TMC acts as a hemilabile...

Efficient Biomimetic Hydroxylation Catalysis witha Bis(pyrazolyl)imidazolylmethane Copper Peroxide Complex

Author Dr. Claudia Wilfer, Patricia Liebhäuser, Dr. Alexander Hoffmann, Hannes Erdmann, Oleg Grossmann, Leander Runtsch, Eva Paffenholz, Rahel Schepper, Regina Dick, Prof. Dr. Matthias Bauer, Maximilian Dürr, Prof. Dr. Ivana Ivanović-Burmazović, Prof. Dr. Sonja Herres-Pawlis Ludwig-Maximilians-Universität München, (Germany) Chem. Eur. J. 2015, 21,1 DOI:  10.1002/chem.201501685 Abstract Bis(pyrazolyl)methane ligands are excellent components of model complexes used to investigate the activity of the enzyme tyrosinase. Combining the N donors 3- tert -butylpyrazole and 1-methylimidazole results in a ligand that is capable of stabilising a (μ-η 2 :η 2 )-dicopper(II) core that resembles the active centre of tyrosinase. UV/Vis spectroscopy shows blueshifted UV bands in comparison to other known peroxo complexes, due to donor competition from different ligand substituents. This effect was investigated with the help of theoretical calculations, including DFT and natural transiti...

Synergistic Stereocontrol in the Enantioselective Ruthenium-Catalyzed Sulfoxidation of Spirodithiolane-Indolones

Dr. Fangrui Zhong, Dr. Alexander Pöthig and Prof. Dr. Thorsten Bach* Article first published online: 10 JUN 2015 Department Chemie and Catalysis Research Center (CRC), Technische Universität München, Lichtenbergstr. 4, 85747 Garching DOI: 10.1002/chem.201501780 View Full Article with Supporting Information (HTML)   Enhanced Article (HTML)   Get PDF (421K) Abstract A chiral ruthenium catalyst was developed for the enantioselective sulfoxidation of the title compounds. The catalyst combines two elements of chirality, a chiral pybox ligand and a chiral bicylic lactam unit, to which the ligand is attached. The latter unit was shown to improve significantly the performance of the catalyst by exposing one of the two enantiotopic sulfur atoms to the active site via hydrogen-bond mediated coordination. Ten differently substituted substrates were converted into the respective sulfoxides in yields of 52–71 % and with ≥90 % ee. 酸化剤は、PhI(OPiv)2、 or  クメンヒドロペルオキシ...

Tailoring RuII Pyridine/Triazole Oxygenation Catalysts and Using Photoreactivity to Probe their Electronic Properties

tmpaのPyをトリアゾールに置き換えたリガンドを持ったRu錯体を作って、mCPBAによるシクロオクテンの水酸化反応に 使っています。 Fritz Weisser,  Hendrik Stevens,  Johannes Klein,  Margarethe van der Meer,  Dr. Stephan Hohloch and Prof. Dr. Biprajit Sarkar * Author Information Institute of Chemistry and Biochemistry, Freie Universität Berlin, Fabeckstrasse 34–36, 14195 Berlin (Germany) Email:  Prof. Dr. Biprajit Sarkar (biprajit.sarkar@fu-berlin.de) * Institute of Chemistry and Biochemistry, Freie Universität Berlin, Fabeckstrasse 34–36, 14195 Berlin (Germany) Article first published online: 8 MAY 2015 DOI: 10.1002/chem.201406441 Abstract Tuning of ligand properties is at the heart of influencing chemical reactivity and generating tailor-made catalysts. Herein, three series of complexes [Ru(L)(Cl)(X)]PF 6  (X=DMSO, PPh 3 , or CD 3 CN) with tripodal ligands (L1–L5) containing pyridine and triazole arms are presented. Triazole-for-pyridine substitution and the substituen...

Drug Metabolism by Cytochrome P450 Enzymes: What Distinguishes the Pathways Leading to Substrate Hydroxylation Over Desaturation?

Chemistry - A European Journal  by Li Ji, Abayomi S. Faponle, Matthew G. Quesne, Mala A. Sainna, Jing Zhang, Alicja Franke, Devesh Kumar, Rudi van Eldik, Weiping Liu, Sam P. de Visser  /   25d   //   keep unread  //   hide   //   preview Abstract Cytochrome P450 enzymes are highly versatile biological catalysts in our body that react with a broad range of substrates. Key functions in the liver include the metabolism of drugs and xenobiotics. One particular metabolic pathway that is poorly understood relates to the P450 activation of aliphatic groups leading to either hydroxylation or desaturation pathways. A DFT and QM/MM study has been carried out on the factors that determine the regioselectivity of aliphatic hydroxylation over desaturation of compounds by P450 isozymes. The calculations establish multistate reactivity patterns, whereby the product distributions differ on each of the spin-state surfa...