Article
Chemistry, Multidisciplinary
Mian Guo, Jisheng Zhang, Lina Zhang, Yong-Min Lee, Shunichi Fukuzumi, Wonwoo Nam
Summary: In this study, six manganese(IV)-oxo complexes bearing electron-rich and -deficient porphyrins were synthesized and investigated in various oxidation reactions. The research found a reversed reactivity between the electron-rich and -deficient Mn(IV)-oxo porphyrins in hydrogen atom transfer and oxygen atom transfer reactions at different temperatures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Christopher J. Miller, Yingyue Chang, Christina Wegeberg, Christine J. McKenzie, T. David Waite
Summary: This study demonstrates that the activation of [Fe-III(OH)(tpena)](+) by H2O2 proceeds by the formation of [Fe-III(OOH)(tpena)](+), which undergoes two major reactions to produce HO· and [Fe-IV(O)(tpena)](+). The production of HO· was quantified by a chemiluminescence method, showing that [Fe-IV(O)(tpena)](+) is produced in much larger yields than HO·. Additionally, the study indicates that a reactive high-valent iron-oxo species and HO· can be generated under mild, aqueous ambient conditions, which represents a significant contribution to biomimetic nonheme chemistry in water.
Article
Chemistry, Inorganic & Nuclear
Sandip Munshi, Arup Sinha, Solomon Yiga, Sridhar Banerjee, Reena Singh, Md Kamal Hossain, Matti Haukka, Andrei Felipe Valiati, Ricardo Dagnoni Huelsmann, Edmar Martendal, Rosely Peralta, Fernando Xavier, Ola F. Wendt, Tapan K. Paine, Ebbe Nordlander
Summary: A series of iron(II) complexes with different ligands were isolated and characterized. The steric and electronic factors were found to affect the reactivity of iron(IV)-oxo complexes. The results highlight the importance of ligand environment in controlling the reactivity of these complexes.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Deepika G. Karmalkar, Mi Sook Seo, Yong-Min Lee, Youngsuk Kim, Eunsung Lee, Ritimukta Sarangi, Shunichi Fukuzumi, Wonwoo Nam
Summary: Binding of Lewis acidic metal ions and Bronsted acid at the metal-oxo group enhances reactivity of high-valent metal-oxo complexes in oxidation reactions. The synthesis, characterization, and reactivity studies of a mononuclear manganese(IV)-oxo complex binding triflic acid were reported in this study. Results show an interesting correlation between the Mn-O stretching frequencies and the reactivities in hydrogen atom transfer and oxygen atom transfer reactions.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jindou Yang, Hai T. Dong, Mi Sook Seo, Virginia A. Larson, Yong-Min Lee, Jason Shearer, Nicolai Lehnert, Wonwoo Nam
Summary: This research reports the preparation, spectroscopic characterization, and reactivity studies of a Co(IV)-oxo complex with an N4-macrocyclic coligand. Experimental data show the formation of a Co(IV) intermediate and the existence of the oxo group, supported by DFT calculations and spectroscopic techniques analyzing the structure.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Wenjuan Zhu, Namita Sharma, Yong-Min Lee, Mohamed E. El-Khouly, Shunichi Fukuzumi, Wonwoo Nam
Summary: This study reports a new method for generating a nonheme iron(IV)-oxo complex using singlet oxygen instead of triplet oxygen and a hydrogen atom donor with relatively strong C-H bonds.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Priya Singh, Eleanor Stewart-Jones, Melissa C. Denler, Timothy A. Jackson
Summary: High-valent metal-oxo intermediates play a crucial role in oxygen-atom transfer reactions, and changes in metal reduction potential can lead to variations in reaction mechanisms. The rate variations observed for Mn-IV-oxo complexes are primarily controlled by activation enthalpy, indicating a single-step OAT mechanism. This suggests that large variations in sulfoxidation by Mn-IV-oxo centers occur without a change in reaction mechanism.
DALTON TRANSACTIONS
(2021)
Editorial Material
Chemistry, Multidisciplinary
Dipankar Sahoo, Diana A. Iovan
Summary: A recent study reported the isolation and characterization of an N-trifluoromethyl-substituted Fe(IV) bisimido species that undergoes intramolecular C-H activation. This discovery opens up new possibilities for N-group-transfer chemistry.
Article
Chemistry, Multidisciplinary
Jin Lin, Qiangsheng Sun, Wei Sun
Summary: The hydroxylation of hexane by two (FeO)-O-IV complexes with pentadentate and tetradentate ligands derived from l-proline was studied using DFT calculations, which showed that both complexes have triplet ground states. The hydrogen atom abstraction processes by both species proceed through a two-state reactivity, indicating that HAA occurs via a low-barrier quintet surface. Additionally, beyond the rebound step, the dissociation path after HAA was also calculated to potentially occur.
Article
Chemistry, Inorganic & Nuclear
Priya Singh, Melissa C. Denler, Jaycee R. Mayfield, Timothy A. Jackson
Summary: This study investigates the chemoselectivity of Mn-IV-oxo complexes in olefin oxidation and reveals that the selectivity is controlled by the dissociation free energy of the Mn=O bond and the allylic C-H bond.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Krzesimir Korona, Arkadiusz Kornowicz, Iwona Justyniak, Michal Terlecki, Artur Blachowski, Janusz Lewinski
Summary: This study reports on the reactivity between CO2 and V(ii) and Fe(ii) complexes, leading to the preparation of three novel complexes through multiple insertions of CO2. The study provides the first well-documented studies of CO2 reactivity towards the V-N bond and expands the research in this field. Additionally, the study shows that the efficiency of the CO2 insertion processes depends on solvent characteristics (for the Fe(ii) system) and the metal center's coordination sphere geometry (for the V(ii) system).
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Lovleen Kaur, Debasish Mandal
Summary: This article presents a comprehensive density functional theory (DFT) investigation on the role of equatorial sulfur ligation in C-H activation. The study reveals that reactivity increases successively with the enrichment of equatorial sulfur atoms, and computational predictions suggest the synthesis of sulfur-ligated bio-inspired complexes would be more favorable than nitrogen-exclusive ones.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Guilherme L. Tripodi, Magda M. J. Dekker, Jana Roithova, Lawrence Que
Summary: Reactivity of non-heme iron(IV)-oxo complexes is mainly controlled by the ligands, with complexes featuring tetradentate ligands showing the highest reactivity. Fine-tuning of the reactivity of these complexes can be achieved by attaching additional ligands in solution, with the ArIO oxidant playing a previously unknown role. The reactivity of the complexes correlates with the Fe=O and FeO-H stretching vibrations, with the most reactive complex in the series having the weakest Fe=O bond and forming the strongest FeO-H bond.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Mahmud Abu-Odeh, Katharina Bleher, Neethinathan Johnee Britto, Peter Comba, Michael Gast, Madhavan Jaccob, Marion Kerscher, Saskia Krieg, Marius Kurth
Summary: The study reveals the highly reactive nature of the nonheme iron(IV)-oxido complex, with substrate oxidation significantly faster than self-decay processes. Intermediate formed during C-H abstraction reactions can produce products but with a long lifetime leading to unproductive reactions in some cases.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Xuanyu Cao, Huiling Song, Xiao-Xi Li, Qing-An Qiao, Yufen Zhao, Yong Wang
Summary: This study investigates the mechanistic details of the iron hydroperoxo and oxo-iron hydroxyl species as intermediates in 2-oxoglutarate dependent dioxygenases using density functional theory calculations. The results reveal significant differences in structure and conversion between these two species. The iron hydroperoxo species does not act as the oxidant and readily decays to the oxo-iron hydroxyl species.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Caiyun Geng, Thomas Weiske, Jilai Li, Sason Shaik, Helmut Schwarz
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Physical
Xiaoli Sun, Caiyun Geng, Jilai Li
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2019)
Correction
Chemistry, Multidisciplinary
Caiyun Geng, Thomas Weiske, Jilai Li, Sason Shaik, Helmut Schwarz
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Physical
Tian Tian, Xiaoli Sun, Thomas Weiske, Yuxi Cai, Caiyun Geng, Jilai Li, Helmut Schwarz
Article
Chemistry, Multidisciplinary
Caiyun Geng, Jilai Li, Thomas Weiske, Helmut Schwarz
CHEMISTRY-A EUROPEAN JOURNAL
(2019)
Article
Multidisciplinary Sciences
Caiyun Geng, Jilai Li, Thomas Weiske, Helmut Schwarz
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2019)
Article
Nanoscience & Nanotechnology
Zhiliang Chen, Xiaojie Liu, Chuixiu Huang, Jilai Li, Xiantao Shen
ACS APPLIED MATERIALS & INTERFACES
(2020)
Article
Chemistry, Multidisciplinary
Jilai Li, Caiyun Geng, Thomas Weiske, Helmut Schwarz
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Jilai Li, Caiyun Geng, Thomas Weiske, Helmut Schwarz
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Jilai Li, Caiyun Geng, Thomas Weiske, Mingfei Zhou, Jun Li, Helmut Schwarz
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Physical
Jose M. Mercero, Elixabete Rezabal, Jesus M. Ugalde, Thomas Weiske, Jilai Li
Summary: Using Fourier-transform ion cyclotron resonance mass spectrometry, it was experimentally determined that Sc+ reacts with SO2 in the gas phase to form ScO+ and SO. Quantum chemical calculations confirmed the exoergic nature of the multi-step process and the energetically favorable intermediates and transition states. The oxygen exchange reaction between ScO+ and SO2 is facilitated by the formation of a highly symmetric cyclic intermediate.