Deeper Understanding of Mononuclear Manganese(IV)–Oxo Binding Brønsted and Lewis Acids and the Manganese(IV)–Hydroxide Complex

Karmalkar, Deepika G.; Seo, Mi Sook; Lee, Yong-Min; Kim, Youngsuk; Lee, Eunsung; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

doi:10.1021/acs.inorgchem.1c02119

Title: Deeper Understanding of Mononuclear Manganese(IV)–Oxo Binding Brønsted and Lewis Acids and the Manganese(IV)–Hydroxide Complex

Journal Article · Wed Oct 27 00:00:00 EDT 2021 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.1c02119· OSTI ID:1878521

^[1];

^[2];

^[3];

^[1];

^[1]

Ewha Womans Univ., Seoul (Korea, Republic of)
Pohang Univ. of Science and Technology (POSTECH) (Korea, Republic of)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Stanford Univ., CA (United States)

Binding of Lewis acidic metal ions and Brønsted acid at the metal–oxo group of high-valent metal–oxo complexes enhances their reactivities significantly in oxidation reactions. However, such a binding of Lewis acids and proton at the metal–oxo group has been questioned in several cases and remains to be clarified. In this work, we report the synthesis, characterization, and reactivity studies of a mononuclear manganese(IV)–oxo complex binding triflic acid, {[(dpaq)Mn^IV(O)]–HOTf}⁺ (1–HOTf). First, 1–HOTf was synthesized and characterized using various spectroscopic techniques, including resonance Raman (rRaman) and X-ray absorption spectroscopy/extended X-ray absorption fine structure. In particular, in rRaman experiments, we observed a linear correlation between the Mn–O stretching frequencies of 1–HOTf (e.g., ν_Mn–O at ~793 cm^–1) and 1–Mⁿ⁺ (Mn⁺ = Ca²⁺, Zn²⁺, Lu³⁺, Al³⁺, or Sc³⁺) and the Lewis acidities of H⁺ and Mⁿ⁺ ions, suggesting that H+ and Mn+ bind at the metal–oxo moiety of [(dpaq)Mn^IV(O)]⁺. Interestingly, a single-crystal structure of 1–HOTf was obtained by X-ray diffraction analysis, but the structure was not an expected Mn(IV)–oxo complex but a Mn(IV)–hydroxide complex, [(dpaq)Mn^IV(OH)](OTf)₂ (4), with a Mn–O bond distance of 1.8043(19) Å and a Mn–O stretch at 660 cm^–1. More interestingly, 4 reverted to 1–HOTf upon dissolution, demonstrating that 1–HOTf and 4 are interconvertible depending on the physical states, such as 1–HOTf in solution and 4 in isolated solid. The reactivity of 1–HOTf was investigated in hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) reactions and then compared with those of 1–Mn+ complexes; an interesting correlation between the Mn–O stretching frequencies of 1–HOTf and 1–Mⁿ⁺ and their reactivities in the OAT and HAT reactions is reported for the first time in this study.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); National Research Foundation of Korea (NRF); National Institutes of Health (NIH)

Grant/Contract Number:: AC02-76SF00515; NRF-2021R1A3B1076539; 2020R1I1A1A01074630; 2019R1I1A1A01055822; P30GM133894

OSTI ID:: 1878521

Journal Information:: Inorganic Chemistry, Vol. 60, Issue 22; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (128)

Concerted proton–electron transfer reactions of manganese–hydroxo and manganese–oxo complexes Mayfield, Jaycee R.; Grotemeyer, Elizabeth N.; Jackson, Timothy A. Chemical Communications, Vol. 56, Issue 65 https://doi.org/10.1039/D0CC01201G	journal	January 2020
Brønsted Acid-Promoted C–H Bond Cleavage via Electron Transfer from Toluene Derivatives to a Protonated Nonheme Iron(IV)-Oxo Complex with No Kinetic Isotope Effect Park, Jiyun; Lee, Yong-Min; Nam, Wonwoo Journal of the American Chemical Society, Vol. 135, Issue 13 https://doi.org/10.1021/ja311662w	journal	March 2013
Dioxygen Activation by Metalloenzymes and Models Nam, Wonwoo Accounts of Chemical Research, Vol. 40, Issue 7 https://doi.org/10.1021/ar700131d	journal	July 2007
Unified View of Oxidative C–H Bond Cleavage and Sulfoxidation by a Nonheme Iron(IV)–Oxo Complex via Lewis Acid-Promoted Electron Transfer Park, Jiyun; Morimoto, Yuma; Lee, Yong-Min Inorganic Chemistry, Vol. 53, Issue 7 https://doi.org/10.1021/ic403124u	journal	March 2014
Kinetic Isotope Effect Determination Probes the Spin of the Transition State, Its Stereochemistry, and Its Ligand Sphere in Hydrogen Abstraction Reactions of Oxoiron(IV) Complexes Mandal, Debasish; Mallick, Dibyendu; Shaik, Sason Accounts of Chemical Research, Vol. 51, Issue 1 https://doi.org/10.1021/acs.accounts.7b00442	journal	January 2018
Redox inactive metal ion triggered N-dealkylation by an iron catalyst with dioxygen activation: a lesson from lipoxygenases Zhang, Jisheng; Wang, Yujuan; Luo, Nengchao Dalton Transactions, Vol. 44, Issue 21 https://doi.org/10.1039/C5DT00804B	journal	January 2015
A Mononuclear Non-Heme Manganese(IV)–Oxo Complex Binding Redox-Inactive Metal Ions Chen, Junying; Lee, Yong-Min; Davis, Katherine M. Journal of the American Chemical Society, Vol. 135, Issue 17 https://doi.org/10.1021/ja312113p	journal	January 2013
Spectroscopic Identification of an Fe ^III Center, not Fe ^IV , in the Crystalline Sc–O–Fe Adduct Derived from [Fe ^IV (O)(TMC)] ²⁺ Prakash, Jai; Rohde, Gregory T.; Meier, Katlyn K. Journal of the American Chemical Society, Vol. 137, Issue 10 https://doi.org/10.1021/jacs.5b00535	journal	March 2015
Evidence for an oxygen evolving iron–oxo–cerium intermediate in iron-catalysed water oxidation Codolà, Zoel; Gómez, Laura; Kleespies, Scott T. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms6865	journal	January 2015
High-Valent Manganese–Oxo Valence Tautomers and the Influence of Lewis/Brönsted Acids on C–H Bond Cleavage Baglia, Regina A.; Krest, Courtney M.; Yang, Tzuhsiung Inorganic Chemistry, Vol. 55, Issue 20 https://doi.org/10.1021/acs.inorgchem.6b02109	journal	September 2016
The development of molecular water oxidation catalysts Matheu, Roc; Garrido-Barros, Pablo; Gil-Sepulcre, Marcos Nature Reviews Chemistry, Vol. 3, Issue 5 https://doi.org/10.1038/s41570-019-0096-0	journal	April 2019
Tuning the reactivity of mononuclear nonheme manganese( iv )-oxo complexes by triflic acid Chen, Junying; Yoon, Heejung; Lee, Yong-Min Chemical Science, Vol. 6, Issue 6 https://doi.org/10.1039/C5SC00535C	journal	January 2015
Lewis-Acid-Promoted Stoichiometric and Catalytic Oxidations by Manganese Complexes Having Cross-Bridged Cyclam Ligand: A Comprehensive Study Dong, Lei; Wang, Yujuan; Lv, Yanzong Inorganic Chemistry, Vol. 52, Issue 9 https://doi.org/10.1021/ic400361s	journal	April 2013
Crystal structure of oxygen-evolving photosystem II at a resolution of 1.9 Å Umena, Yasufumi; Kawakami, Keisuke; Shen, Jian-Ren Nature, Vol. 473, Issue 7345 https://doi.org/10.1038/nature09913	journal	April 2011
Transient Intermediates from Mn(salen) with Sterically Hindered Mesityl Groups: Interconversion between Mn ^IV -Phenolate and Mn ^III -Phenoxyl Radicals as an Origin for Unique Reactivity Kurahashi, Takuya; Kikuchi, Akihiro; Tosha, Takehiko Inorganic Chemistry, Vol. 47, Issue 5 https://doi.org/10.1021/ic702061y	journal	March 2008
Metal ion-coupled and decoupled electron transfer Fukuzumi, Shunichi; Ohkubo, Kei Coordination Chemistry Reviews, Vol. 254, Issue 3-4 https://doi.org/10.1016/j.ccr.2009.10.020	journal	February 2010
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
A new look at the role of thiolate ligation in cytochrome P450 Yosca, Timothy H.; Ledray, Aaron P.; Ngo, Joanna JBIC Journal of Biological Inorganic Chemistry, Vol. 22, Issue 2-3 https://doi.org/10.1007/s00775-016-1430-3	journal	January 2017
Effect of Lewis Acids on the Structure and Reactivity of a Mononuclear Hydroxomanganese(III) Complex Rice, Derek B.; Grotemeyer, Elizabeth N.; Donovan, Anna M. Inorganic Chemistry, Vol. 59, Issue 5 https://doi.org/10.1021/acs.inorgchem.9b02980	journal	February 2020
Theoretical x-ray absorption fine structure standards Rehr, J. J.; Mustre de Leon, J.; Zabinsky, S. I. Journal of the American Chemical Society, Vol. 113, Issue 14 https://doi.org/10.1021/ja00014a001	journal	July 1991
Lewis Acid Coupled Electron Transfer of Metal-Oxygen Intermediates Fukuzumi, Shunichi; Ohkubo, Kei; Lee, Yong-Min Chemistry - A European Journal, Vol. 21, Issue 49 https://doi.org/10.1002/chem.201502693	journal	September 2015
Oxidation Reactions with Bioinspired Mononuclear Non-Heme Metal-Oxo Complexes Engelmann, Xenia; Monte-Pérez, Inés; Ray, Kallol Angewandte Chemie International Edition, Vol. 55, Issue 27 https://doi.org/10.1002/anie.201600507	journal	June 2016
High-valent metal-oxo intermediates in energy demanding processes: from dioxygen reduction to water splitting Ray, Kallol; Heims, Florian; Schwalbe, Matthias Current Opinion in Chemical Biology, Vol. 25 https://doi.org/10.1016/j.cbpa.2015.01.014	journal	April 2015
SHELXT – Integrated space-group and crystal-structure determination Sheldrick, George M. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053273314026370	journal	January 2015
Catalytic control of electron-transfer processes Fukuzumi, Shunichi Pure and Applied Chemistry, Vol. 75, Issue 5 https://doi.org/10.1351/pac200375050577	journal	January 2003
Lewis versus Brønsted Acid Activation of a Mn(IV) Catalyst for Alkene Oxidation Steen, Jorn D.; Stepanovic, Stepan; Parvizian, Mahsa Inorganic Chemistry, Vol. 58, Issue 21 https://doi.org/10.1021/acs.inorgchem.9b02737	journal	October 2019
Facile and Reversible Formation of Iron(III)-Oxo-Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III) Draksharapu, Apparao; Rasheed, Waqas; Klein, Johannes E. M. N. Angewandte Chemie International Edition, Vol. 56, Issue 31 https://doi.org/10.1002/anie.201704322	journal	June 2017
Mechanistic insight into oxygen atom transfer reactions by mononuclear manganese( iv )–oxo adducts Singh, Priya; Stewart-Jones, Eleanor; Denler, Melissa C. Dalton Transactions, Vol. 50, Issue 10 https://doi.org/10.1039/D0DT04436A	journal	January 2021
Redox Reactivity of a Mononuclear Manganese-Oxo Complex Binding Calcium Ion and Other Redox-Inactive Metal Ions Sankaralingam, Muniyandi; Lee, Yong-Min; Pineda-Galvan, Yuliana Journal of the American Chemical Society, Vol. 141, Issue 3 https://doi.org/10.1021/jacs.8b11492	journal	December 2018
A change in the oxidation state of iron: scandium is not innocent Swart, Marcel Chemical Communications, Vol. 49, Issue 59 https://doi.org/10.1039/c3cc42200c	journal	January 2013
Evidence for a Precursor Complex in CH Hydrogen Atom Transfer Reactions Mediated by a Manganese(IV) Oxo Complex Garcia-Bosch, Isaac; Company, Anna; Cady, Clyde W. Angewandte Chemie International Edition, Vol. 50, Issue 25 https://doi.org/10.1002/anie.201100907	journal	April 2011
Long-Lived Photoexcited State of a Mn(IV)-Oxo Complex Binding Scandium Ions That is Capable of Hydroxylating Benzene Sharma, Namita; Jung, Jieun; Ohkubo, Kei Journal of the American Chemical Society, Vol. 140, Issue 27 https://doi.org/10.1021/jacs.8b04904	journal	June 2018
Determination of the Cu(III)–OH Bond Distance by Resonance Raman Spectroscopy Using a Normalized Version of Badger’s Rule Spaeth, Andrew D.; Gagnon, Nicole L.; Dhar, Debanjan Journal of the American Chemical Society, Vol. 139, Issue 12 https://doi.org/10.1021/jacs.7b00210	journal	March 2017
Valence Tautomerism in a High-Valent Manganese–Oxo Porphyrinoid Complex Induced by a Lewis Acid Leeladee, Pannee; Baglia, Regina A.; Prokop, Katharine A. Journal of the American Chemical Society, Vol. 134, Issue 25 https://doi.org/10.1021/ja304609n	journal	June 2012
BF ₃ -Activated Oxidation of Alkanes by MnO ₄ ^- Lam, William W. Y.; Yiu, Shek-Man; Lee, Joyce M. N. Journal of the American Chemical Society, Vol. 128, Issue 9 https://doi.org/10.1021/ja0552951	journal	February 2006
Fine Control of the Redox Reactivity of a Nonheme Iron(III)-Peroxo Complex by Binding Redox-Inactive Metal Ions Bae, Seong Hee; Lee, Yong-Min; Fukuzumi, Shunichi Angewandte Chemie International Edition, Vol. 56, Issue 3 https://doi.org/10.1002/anie.201610828	journal	December 2016
The Effects of Redox-Inactive Metal Ions on the Activation of Dioxygen: Isolation and Characterization of a Heterobimetallic Complex Containing a Mn ^III –(μ-OH)–Ca ^II Core Park, Young Jun; Ziller, Joseph W.; Borovik, A. S. Journal of the American Chemical Society, Vol. 133, Issue 24 https://doi.org/10.1021/ja203458d	journal	June 2011
Progress Toward a Molecular Mechanism of Water Oxidation in Photosystem II Vinyard, David J.; Brudvig, Gary W. Annual Review of Physical Chemistry, Vol. 68, Issue 1 https://doi.org/10.1146/annurev-physchem-052516-044820	journal	May 2017
A Synthetic Model of the Mn3Ca Subsite of the Oxygen-Evolving Complex in Photosystem II Kanady, J. S.; Tsui, E. Y.; Day, M. W. Science, Vol. 333, Issue 6043 https://doi.org/10.1126/science.1206036	journal	August 2011
Redox-inactive metals modulate the reduction potential in heterometallic manganese–oxido clusters Tsui, Emily Y.; Tran, Rosalie; Yano, Junko Nature Chemistry, Vol. 5, Issue 4 https://doi.org/10.1038/nchem.1578	journal	March 2013
Tuning Reactivity and Mechanism in Oxidation Reactions by Mononuclear Nonheme Iron(IV)-Oxo Complexes Nam, Wonwoo; Lee, Yong-Min; Fukuzumi, Shunichi Accounts of Chemical Research, Vol. 47, Issue 4 https://doi.org/10.1021/ar400258p	journal	February 2014
PySpline: A Modern, Cross-Platform Program for the Processing of Raw Averaged XAS Edge and EXAFS Data Tenderholt, Adam; Hedman, Britt; Hodgson, Keith O. X-RAY ABSORPTION FINE STRUCTURE - XAFS13: 13th International Conference, AIP Conference Proceedings https://doi.org/10.1063/1.2644442	conference	January 2007
Unified Mechanism of Oxygen Atom Transfer and Hydrogen Atom Transfer Reactions with a Triflic Acid-Bound Nonheme Manganese(IV)–Oxo Complex via Outer-Sphere Electron Transfer Lee, Yong-Min; Kim, Surin; Ohkubo, Kei Journal of the American Chemical Society, Vol. 141, Issue 6 https://doi.org/10.1021/jacs.8b12935	journal	January 2019
60 years of dioxygen activation Que, Lawrence JBIC Journal of Biological Inorganic Chemistry, Vol. 22, Issue 2-3 https://doi.org/10.1007/s00775-017-1443-6	journal	February 2017
Characterization of a selenocysteine-ligated P450 compound I reveals direct link between electron donation and reactivity Onderko, Elizabeth L.; Silakov, Alexey; Yosca, Timothy H. Nature Chemistry, Vol. 9, Issue 7 https://doi.org/10.1038/nchem.2781	journal	May 2017
Formation of superoxide–metal ion complexes and the electron transfer catalysis Fukuzumi, Shunichi; Ohtsu, Hideki; Ohkubo, Kei Coordination Chemistry Reviews, Vol. 226, Issue 1-2 https://doi.org/10.1016/S0010-8545(01)00435-0	journal	March 2002
Strong Inhibition of O-Atom Transfer Reactivity for Mn ^IV (O)(π-Radical-Cation)(Lewis Acid) versus Mn ^V (O) Porphyrinoid Complexes Zaragoza, Jan Paulo T.; Baglia, Regina A.; Siegler, Maxime A. Journal of the American Chemical Society, Vol. 137, Issue 20 https://doi.org/10.1021/jacs.5b00875	journal	May 2015
Activation of Metal Oxo and Nitrido Complexes by Lewis Acids Liu, Yingying; Lau, Tai-Chu Journal of the American Chemical Society, Vol. 141, Issue 9 https://doi.org/10.1021/jacs.8b13100	journal	February 2019
ESR Spectra of Superoxide Anion−Scandium Complexes Detectable in Fluid Solution Fukuzumi, Shunichi; Patz, Matthias; Suenobu, Tomoyoshi Journal of the American Chemical Society, Vol. 121, Issue 7 https://doi.org/10.1021/ja981289b	journal	February 1999
Toward the Synthesis of More Reactive S = 2 Non-Heme Oxoiron(IV) Complexes Puri, Mayank; Que, Lawrence Accounts of Chemical Research, Vol. 48, Issue 8 https://doi.org/10.1021/acs.accounts.5b00244	journal	July 2015
Significantly shorter Fe–S bond in cytochrome P450-I is consistent with greater reactivity relative to chloroperoxidase Krest, Courtney M.; Silakov, Alexey; Rittle, Jonathan Nature Chemistry, Vol. 7, Issue 9 https://doi.org/10.1038/nchem.2306	journal	August 2015
The O ₂ -Evolving Complex of Photosystem II: Recent Insights from Quantum Mechanics/Molecular Mechanics (QM/MM), Extended X-ray Absorption Fine Structure (EXAFS), and Femtosecond X-ray Crystallography Data Askerka, Mikhail; Brudvig, Gary W.; Batista, Victor S. Accounts of Chemical Research, Vol. 50, Issue 1 https://doi.org/10.1021/acs.accounts.6b00405	journal	December 2016
Effects of Noncovalent Interactions on High-Spin Fe(IV)–Oxido Complexes Oswald, Victoria F.; Lee, Justin L.; Biswas, Saborni Journal of the American Chemical Society, Vol. 142, Issue 27 https://doi.org/10.1021/jacs.0c03085	journal	June 2020
Multiple-scattering calculations of x-ray-absorption spectra Zabinsky, S. I.; Rehr, J. J.; Ankudinov, A. Physical Review B, Vol. 52, Issue 4 https://doi.org/10.1103/PhysRevB.52.2995	journal	July 1995
Mechanisms of metal ion-coupled electron transfer Fukuzumi, Shunichi; Ohkubo, Kei; Morimoto, Yuma Physical Chemistry Chemical Physics, Vol. 14, Issue 24 https://doi.org/10.1039/c2cp40459a	journal	January 2012
Biomimetic Reactivity of Oxygen-Derived Manganese and Iron Porphyrinoid Complexes Baglia, Regina A.; Zaragoza, Jan Paulo T.; Goldberg, David P. Chemical Reviews, Vol. 117, Issue 21 https://doi.org/10.1021/acs.chemrev.7b00180	journal	October 2017
A synthetic Mn4Ca-cluster mimicking the oxygen-evolving center of photosynthesis Zhang, C.; Chen, C.; Dong, H. Science, Vol. 348, Issue 6235 https://doi.org/10.1126/science.aaa6550	journal	May 2015
Lessons from Nature: A Bio-Inspired Approach to Molecular Design Cook, Sarah A.; Hill, Ethan A.; Borovik, A. S. Biochemistry, Vol. 54, Issue 27 https://doi.org/10.1021/acs.biochem.5b00249	journal	June 2015
Metal Ion-coupled Electron-transfer Reduction of Dioxygen Fukuzumi, Shunichi Chemistry Letters, Vol. 37, Issue 8 https://doi.org/10.1246/cl.2008.808	journal	August 2008
Oxoiron(IV) in Chloroperoxidase Compound II Is Basic: Implications for P450 Chemistry Green, M. T. Science, Vol. 304, Issue 5677 https://doi.org/10.1126/science.1096897	journal	June 2004
Molecular Catalysts for Water Oxidation Blakemore, James D.; Crabtree, Robert H.; Brudvig, Gary W. Chemical Reviews, Vol. 115, Issue 23 https://doi.org/10.1021/acs.chemrev.5b00122	journal	July 2015
Nonredox Metal Ions Promoted Olefin Epoxidation by Iron(II) Complexes with H ₂ O ₂ : DFT Calculations Reveal Multiple Channels for Oxygen Transfer Zhang, Jisheng; Wei, Wen-Jie; Lu, Xiaoyan Inorganic Chemistry, Vol. 56, Issue 24 https://doi.org/10.1021/acs.inorgchem.7b02463	journal	November 2017
Iron and manganese oxo complexes, oxo wall and beyond Larson, Virginia A.; Battistella, Beatrice; Ray, Kallol Nature Reviews Chemistry, Vol. 4, Issue 8 https://doi.org/10.1038/s41570-020-0197-9	journal	July 2020
Reduction potentials of heterometallic manganese-oxido cubane complexes modulated by redox-inactive metals Tsui, E. Y.; Agapie, T. Proceedings of the National Academy of Sciences, Vol. 110, Issue 25 https://doi.org/10.1073/pnas.1302677110	journal	June 2013
Quantitative Evaluation of Lewis Acidity of Metal Ions with Different Ligands and Counterions in Relation to the Promoting Effects of Lewis Acids on Electron Transfer Reduction of Oxygen Ohkubo, Kei; Menon, Saija C.; Orita, Akihiro The Journal of Organic Chemistry, Vol. 68, Issue 12 https://doi.org/10.1021/jo034258u	journal	June 2003
C−H Bond Activation by a Ferric Methoxide Complex: Modeling the Rate-Determining Step in the Mechanism of Lipoxygenase Goldsmith, Christian R.; Jonas, Robert T.; Stack, T. Daniel P. Journal of the American Chemical Society, Vol. 124, Issue 1 https://doi.org/10.1021/ja016451g	journal	January 2002
Metal Ion-Coupled Electron Transfer of a Nonheme Oxoiron(IV) Complex: Remarkable Enhancement of Electron-Transfer Rates by Sc ³⁺ Morimoto, Yuma; Kotani, Hiroaki; Park, Jiyun Journal of the American Chemical Society, Vol. 133, Issue 3 https://doi.org/10.1021/ja109056x	journal	January 2011
Switchover of the Mechanism between Electron Transfer and Hydrogen-Atom Transfer for a Protonated Manganese(IV)-Oxo Complex by Changing Only the Reaction Temperature Jung, Jieun; Kim, Surin; Lee, Yong-Min Angewandte Chemie International Edition, Vol. 55, Issue 26 https://doi.org/10.1002/anie.201602460	journal	May 2016
Oxomanganese(IV) porphyrins identified by resonance Raman and infrared spectroscopy. Weak bonds and the stability of the half-filled t2g subshell Czernuszewicz, Roman S.; Su, Y. Oliver.; Stern, Michael K. Journal of the American Chemical Society, Vol. 110, Issue 13 https://doi.org/10.1021/ja00221a010	journal	June 1988
Ab initio curved-wave x-ray-absorption fine structure Mustre de Leon, J.; Rehr, J. J.; Zabinsky, S. I. Physical Review B, Vol. 44, Issue 9 https://doi.org/10.1103/PhysRevB.44.4146	journal	September 1991
A High‐Valent Manganese(IV)–Oxo–Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity Karmalkar, Deepika G.; Sankaralingam, Muniyandi; Seo, Mi Sook Angewandte Chemie International Edition, Vol. 58, Issue 45 https://doi.org/10.1002/anie.201910032	journal	November 2019
Water-oxidizing complex in Photosystem II: Its structure and relation to manganese-oxide based catalysts Najafpour, Mohammad Mahdi; Zaharieva, Ivelina; Zand, Zahra Coordination Chemistry Reviews, Vol. 409 https://doi.org/10.1016/j.ccr.2020.213183	journal	May 2020
Oxidation of Naphthalene with a Manganese(IV) Bis(hydroxo) Complex in the Presence of Acid Jeong, Donghyun; Yan, James J.; Noh, Hyeonju Angewandte Chemie International Edition, Vol. 57, Issue 26 https://doi.org/10.1002/anie.201802641	journal	May 2018
Iron(IV)hydroxide pKa and the Role of Thiolate Ligation in C-H Bond Activation by Cytochrome P450 Yosca, T. H.; Rittle, J.; Krest, C. M. Science, Vol. 342, Issue 6160 https://doi.org/10.1126/science.1244373	journal	November 2013
Fluorescence Maxima of 10-Methylacridone−Metal Ion Salt Complexes: A Convenient and Quantitative Measure of Lewis Acidity of Metal Ion Salts Fukuzumi, Shunichi; Ohkubo, Kei Journal of the American Chemical Society, Vol. 124, Issue 35 https://doi.org/10.1021/ja026613o	journal	September 2002
Acid Catalysis via Acid‐Promoted Electron Transfer Fukuzumi, Shunichi; Lee, Yong‐Min; Nam, Wonwoo Bulletin of the Korean Chemical Society, Vol. 41, Issue 12 https://doi.org/10.1002/bkcs.12124	journal	November 2020
Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer Fukuzumi, Shunichi; Morimoto, Yuma; Kotani, Hiroaki Nature Chemistry, Vol. 2, Issue 9 https://doi.org/10.1038/nchem.731	journal	July 2010
Synthesis, Characterization, and Solution Properties of a Novel Cross-Bridged Cyclam Manganese(IV) Complex Having Two Terminal Hydroxo Ligands Yin, Guochuan; McCormick, James M.; Buchalova, Maria Inorganic Chemistry, Vol. 45, Issue 20 https://doi.org/10.1021/ic0521123	journal	October 2006
Activation of a Non‐Heme Fe ^III ‐OOH by a Second Fe ^III to Hydroxylate Strong C−H Bonds: Possible Implications for Soluble Methane Monooxygenase Kal, Subhasree; Que, Lawrence Angewandte Chemie International Edition, Vol. 58, Issue 25 https://doi.org/10.1002/anie.201903465	journal	June 2019
Understanding the Oxidative Relationships of the Metal Oxo, Hydroxo, and Hydroperoxide Intermediates with Manganese(IV) Complexes Having Bridged Cyclams: Correlation of the Physicochemical Properties with Reactivity Yin, Guochuan Accounts of Chemical Research, Vol. 46, Issue 2 https://doi.org/10.1021/ar300208z	journal	November 2012
Scandium Ion-Enhanced Oxidative Dimerization and N -Demethylation of N , N -Dimethylanilines by a Non-Heme Iron(IV)-Oxo Complex Park, Jiyun; Morimoto, Yuma; Lee, Yong-Min Inorganic Chemistry, Vol. 50, Issue 22 https://doi.org/10.1021/ic201545a	journal	November 2011
Targeting of High-Valent Iron-TAML Activators at Hydrocarbons and Beyond Collins, Terrence J.; Ryabov, Alexander D. Chemical Reviews, Vol. 117, Issue 13 https://doi.org/10.1021/acs.chemrev.7b00034	journal	March 2017
Synthesis, Structure, and Characterization of a Novel Manganese(IV) Monomer, [Mn ^IV (Me ₃ TACN)(OMe) ₃ ](PF ₆ ) (Me ₃ TACN = N , N ‘, N ‘‘-Trimethyl-1,4,7-triazacyclononane), and Its Activity toward Olefin Oxidation with Hydrogen Peroxide Chin Quee-Smith, Vikki; DelPizzo, Lisa; Jureller, Sharon H. Inorganic Chemistry, Vol. 35, Issue 22 https://doi.org/10.1021/ic951522w	journal	January 1996
Photosynthetic Water Oxidation: Insights from Manganese Model Chemistry Young, Karin J.; Brennan, Bradley J.; Tagore, Ranitendranath Accounts of Chemical Research, Vol. 48, Issue 3 https://doi.org/10.1021/ar5004175	journal	February 2015
Metal ion-coupled electron-transfer reactions of metal-oxygen complexes Devi, Tarali; Lee, Yong-Min; Nam, Wonwoo Coordination Chemistry Reviews, Vol. 410 https://doi.org/10.1016/j.ccr.2020.213219	journal	May 2020
Non-redox metal ion promoted oxygen transfer by a non-heme manganese catalyst Chen, Zhuqi; Yang, Ling; Choe, Cholho Chemical Communications, Vol. 51, Issue 10 https://doi.org/10.1039/C4CC07981G	journal	January 2015
Redox-inactive metal ions modulate the reactivity and oxygen release of mononuclear non-haem iron(III)–peroxo complexes Bang, Suhee; Lee, Yong-Min; Hong, Seungwoo Nature Chemistry, Vol. 6, Issue 10 https://doi.org/10.1038/nchem.2055	journal	September 2014
The Possible Role of Proton-Coupled Electron Transfer (PCET) in Water Oxidation by Photosystem II Meyer, Thomas J.; Huynh, My Hang V.; Thorp, H. Holden Angewandte Chemie International Edition, Vol. 46, Issue 28 https://doi.org/10.1002/anie.200600917	journal	July 2007
The Structure of Photosystem II and the Mechanism of Water Oxidation in Photosynthesis Shen, Jian-Ren Annual Review of Plant Biology, Vol. 66, Issue 1 https://doi.org/10.1146/annurev-arplant-050312-120129	journal	April 2015
Tuning the Geometric and Electronic Structure of Synthetic High-Valent Heme Iron(IV)-Oxo Models in the Presence of a Lewis Acid and Various Axial Ligands Ehudin, Melanie A.; Gee, Leland B.; Sabuncu, Sinan Journal of the American Chemical Society, Vol. 141, Issue 14 https://doi.org/10.1021/jacs.9b00795	journal	March 2019
Formation of the syn isomer of [Fe ^IV (O _anti )(TMC)(NCMe)] ²⁺ in the reaction of Lewis acids with the side-on bound peroxo ligand in [Fe ^III (η ² -O ₂ )(TMC)] ⁺ Prakash, Jai; Que, Lawrence Chemical Communications, Vol. 52, Issue 52 https://doi.org/10.1039/C6CC01660J	journal	January 2016
Factors Controlling the Chemoselectivity in the Oxidation of Olefins by Nonheme Manganese(IV)-Oxo Complexes Kim, Surin; Cho, Kyung-Bin; Lee, Yong-Min Journal of the American Chemical Society, Vol. 138, Issue 33 https://doi.org/10.1021/jacs.6b06252	journal	August 2016
Biological Water Oxidation Cox, Nicholas; Pantazis, Dimitrios A.; Neese, Frank Accounts of Chemical Research, Vol. 46, Issue 7 https://doi.org/10.1021/ar3003249	journal	March 2013
Manganese Compounds as Water-Oxidizing Catalysts: From the Natural Water-Oxidizing Complex to Nanosized Manganese Oxide Structures Najafpour, Mohammad Mahdi; Renger, Gernot; Hołyńska, Małgorzata Chemical Reviews, Vol. 116, Issue 5 https://doi.org/10.1021/acs.chemrev.5b00340	journal	January 2016
Structure validation in chemical crystallography Spek, Anthony L. Acta Crystallographica Section D Biological Crystallography, Vol. 65, Issue 2, p. 148-155 https://doi.org/10.1107/S090744490804362X	journal	January 2009
Structure of photosystem II and substrate binding at room temperature Young, Iris D.; Ibrahim, Mohamed; Chatterjee, Ruchira Nature, Vol. 540, Issue 7633 https://doi.org/10.1038/nature20161	journal	November 2016
Promoting a non-heme manganese complex catalyzed oxygen transfer reaction by both lewis acid and Brønsted acid: Similarities and distinctions Choe, Cholho; Lv, Zhanao; Wu, Yunfeng Molecular Catalysis, Vol. 438 https://doi.org/10.1016/j.mcat.2017.05.030	journal	September 2017
Preparation and properties of an Mn ^IV –hydroxide complex: proton and electron transfer at a mononuclear manganese site and its relationship to the oxygen evolving complex within photosystem II Taguchi, Taketo; Stone, Kari L.; Gupta, Rupal Chem. Sci., Vol. 5, Issue 8 https://doi.org/10.1039/C4SC00453A	journal	January 2014
A Manganese(V)–Oxo Complex: Synthesis by Dioxygen Activation and Enhancement of Its Oxidizing Power by Binding Scandium Ion Hong, Seungwoo; Lee, Yong-Min; Sankaralingam, Muniyandi Journal of the American Chemical Society, Vol. 138, Issue 27 https://doi.org/10.1021/jacs.6b03874	journal	June 2016
Sc ³⁺ (or HClO ₄ ) Activation of a Nonheme Fe ^III –OOH Intermediate for the Rapid Hydroxylation of Cyclohexane and Benzene Kal, Subhasree; Draksharapu, Apparao; Que, Lawrence Journal of the American Chemical Society, Vol. 140, Issue 17 https://doi.org/10.1021/jacs.8b01435	journal	April 2018
Saturation Kinetics in Phenolic O–H Bond Oxidation by a Mononuclear Mn(III)–OH Complex Derived from Dioxygen Wijeratne, Gayan B.; Corzine, Briana; Day, Victor W. Inorganic Chemistry, Vol. 53, Issue 14 https://doi.org/10.1021/ic500943k	journal	June 2014
Electron transfer and catalysis with high-valent metal-oxo complexes Fukuzumi, Shunichi Dalton Transactions, Vol. 44, Issue 15 https://doi.org/10.1039/C5DT00204D	journal	January 2015
Metal Ion Effect on the Switch of Mechanism from Direct Oxygen Transfer to Metal Ion-Coupled Electron Transfer in the Sulfoxidation of Thioanisoles by a Non-Heme Iron(IV)−Oxo Complex Park, Jiyun; Morimoto, Yuma; Lee, Yong-Min Journal of the American Chemical Society, Vol. 133, Issue 14 https://doi.org/10.1021/ja200901n	journal	April 2011
The reactivity of the active metal oxo and hydroxo intermediates and their implications in oxidations Chen, Zhuqi; Yin, Guochuan Chemical Society Reviews, Vol. 44, Issue 5 https://doi.org/10.1039/C4CS00244J	journal	January 2015
Mn ₄ Ca Cluster in Photosynthesis: Where and How Water is Oxidized to Dioxygen Yano, Junko; Yachandra, Vittal Chemical Reviews, Vol. 114, Issue 8 https://doi.org/10.1021/cr4004874	journal	March 2014
Enhanced Rates of C–H Bond Cleavage by a Hydrogen-Bonded Synthetic Heme High-Valent Iron(IV) Oxo Complex Ehudin, Melanie A.; Quist, David A.; Karlin, Kenneth D. Journal of the American Chemical Society, Vol. 141, Issue 32 https://doi.org/10.1021/jacs.9b01253	journal	July 2019
Native structure of photosystem II at 1.95 Å resolution viewed by femtosecond X-ray pulses Suga, Michihiro; Akita, Fusamichi; Hirata, Kunio Nature, Vol. 517, Issue 7532 https://doi.org/10.1038/nature13991	journal	November 2014
NMR Studies of a Mn ^III -hydroxo Adduct Reveal an Equilibrium between Mn ^III -hydroxo and μ-Oxodimanganese(III,III) Species Rice, Derek B.; Jones, Shannon D.; Douglas, Justin T. Inorganic Chemistry, Vol. 57, Issue 13 https://doi.org/10.1021/acs.inorgchem.8b00917	journal	June 2018
Application of Badger's Rule to Heme and Non-Heme Iron−Oxygen Bonds: An Examination of Ferryl Protonation States Green, Michael T. Journal of the American Chemical Society, Vol. 128, Issue 6 https://doi.org/10.1021/ja054074s	journal	February 2006
Light-induced structural changes and the site of O=O bond formation in PSII caught by XFEL Suga, Michihiro; Akita, Fusamichi; Sugahara, Michihiro Nature, Vol. 543, Issue 7643 https://doi.org/10.1038/nature21400	journal	February 2017
Quantitative Evaluation of Lewis Acidity of Metal Ions Derived from theg Values of ESR Spectra of Superoxide: Metal Ion Complexes in Relation to the Promoting Effects in Electron Transfer Reactions Fukuzumi, Shunichi; Ohkubo, Kei Chemistry, Vol. 6, Issue 24 https://doi.org/10.1002/1521-3765(20001215)6:24<4532::AID-CHEM4532>3.0.CO;2-9	journal	December 2000
Influence of Calcium(II) and Chloride on the Oxidative Reactivity of a Manganese(II) Complex of a Cross-Bridged Cyclen Ligand Zhang, Zhan; Coats, Katherine L.; Chen, Zhuqi Inorganic Chemistry, Vol. 53, Issue 22 https://doi.org/10.1021/ic501342c	journal	October 2014
Crystal structure refinement with SHELXL Sheldrick, George M. Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053229614024218	journal	January 2015
Mn K-edge X-ray absorption studies of mononuclear Mn(III)–hydroxo complexes Rice, Derek B.; Wijeratne, Gayan B.; Jackson, Timothy A. JBIC Journal of Biological Inorganic Chemistry, Vol. 22, Issue 8 https://doi.org/10.1007/s00775-017-1501-0	journal	October 2017
Molecular Designs for Controlling the Local Environments around Metal Ions Cook, Sarah A.; Borovik, A. S. Accounts of Chemical Research, Vol. 48, Issue 8 https://doi.org/10.1021/acs.accounts.5b00212	journal	July 2015
Redox-inactive metal ions promoted the catalytic reactivity of non-heme manganese complexes towards oxygen atom transfer Choe, Cholho; Yang, Ling; Lv, Zhanao Dalton Transactions, Vol. 44, Issue 19 https://doi.org/10.1039/C4DT03993A	journal	January 2015
An amphoteric reactivity of a mixed-valent bis(μ-oxo)dimanganese( iii , iv ) complex acting as an electrophile and a nucleophile Sankaralingam, Muniyandi; Jeon, So Hyun; Lee, Yong-Min Dalton Transactions, Vol. 45, Issue 1 https://doi.org/10.1039/C5DT04292E	journal	January 2016
Structure of photosynthetic LH1–RC supercomplex at 1.9 Å resolution Yu, Long-Jiang; Suga, Michihiro; Wang-Otomo, Zheng-Yu Nature, Vol. 556, Issue 7700 https://doi.org/10.1038/s41586-018-0002-9	journal	April 2018
Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins Huang, Xiongyi; Groves, John T. Chemical Reviews, Vol. 118, Issue 5 https://doi.org/10.1021/acs.chemrev.7b00373	journal	December 2017
A Reactive Manganese(IV)–Hydroxide Complex: A Missing Intermediate in Hydrogen Atom Transfer by High-Valent Metal-Oxo Porphyrinoid Compounds Zaragoza, Jan Paulo T.; Siegler, Maxime A.; Goldberg, David P. Journal of the American Chemical Society, Vol. 140, Issue 12 https://doi.org/10.1021/jacs.8b00350	journal	March 2018
A Mononuclear Non-heme Manganese(III)–Aqua Complex as a New Active Oxidant in Hydrogen Atom Transfer Reactions Sankaralingam, Muniyandi; Lee, Yong-Min; Karmalkar, Deepika G. Journal of the American Chemical Society, Vol. 140, Issue 40 https://doi.org/10.1021/jacs.8b07772	journal	September 2018
Heme and Nonheme High-Valent Iron and Manganese Oxo Cores in Biological and Abiological Oxidation Reactions Guo, Mian; Corona, Teresa; Ray, Kallol ACS Central Science, Vol. 5, Issue 1 https://doi.org/10.1021/acscentsci.8b00698	journal	December 2018
Factors Affecting Hydrogen Atom Transfer Reactivity of Metal–Oxo Porphyrinoid Complexes Sacramento, Jireh Joy D.; Goldberg, David P. Accounts of Chemical Research, Vol. 51, Issue 11 https://doi.org/10.1021/acs.accounts.8b00414	journal	October 2018
Mechanistic Borderline of One-Step Hydrogen Atom Transfer versus Stepwise Sc ³⁺ -Coupled Electron Transfer from Benzyl Alcohol Derivatives to a Non-Heme Iron(IV)-Oxo Complex Morimoto, Yuma; Park, Jiyun; Suenobu, Tomoyoshi Inorganic Chemistry, Vol. 51, Issue 18 https://doi.org/10.1021/ic3016723	journal	September 2012
Highly Reactive Manganese(IV)-Oxo Porphyrins Showing Temperature-Dependent Reversed Electronic Effect in C–H Bond Activation Reactions Guo, Mian; Seo, Mi Sook; Lee, Yong-Min Journal of the American Chemical Society, Vol. 141, Issue 31 https://doi.org/10.1021/jacs.9b04496	journal	July 2019
A High Spin Mn(IV)-Oxo Complex Generated via Stepwise Proton and Electron Transfer from Mn(III)–Hydroxo Precursor: Characterization and C–H Bond Cleavage Reactivity Biswas, Sachidulal; Mitra, Amritaa; Banerjee, Sridhar Inorganic Chemistry, Vol. 58, Issue 15 https://doi.org/10.1021/acs.inorgchem.9b00579	journal	July 2019
Preparation and Properties of a Monomeric Mn ^IV −Oxo Complex Parsell, Trenton H.; Behan, Rachel K.; Green, Michael T. Journal of the American Chemical Society, Vol. 128, Issue 27 https://doi.org/10.1021/ja062332v	journal	July 2006
Enhanced Electron-Transfer Reactivity of Nonheme Manganese(IV)–Oxo Complexes by Binding Scandium Ions Yoon, Heejung; Lee, Yong-Min; Wu, Xiujuan Journal of the American Chemical Society, Vol. 135, Issue 24 https://doi.org/10.1021/ja403965h	journal	June 2013

Similar Records

Tuning the reactivity of mononuclear nonheme manganese(iv)-oxo complexes by triflic acid

Journal Article · Tue Apr 14 00:00:00 EDT 2015 · Chemical Science · OSTI ID:1878521

Chen, Junying; Yoon, Heejung; Lee, Yong -Min; +4 more

High-valent manganese–oxo valence tautomers and the influence of Lewis/Brönsted acids on C–H bond cleavage

Journal Article · Fri Sep 30 00:00:00 EDT 2016 · Inorganic Chemistry · OSTI ID:1878521

Baglia, Regina A.; Krest, Courtney M.; Yang, Tzuhsiung; +2 more

A Mononuclear Non-Heme Manganese(IV)-Oxo Complex Binding Redox-Inactive Metal Ions

Journal Article · Wed May 29 00:00:00 EDT 2013 · Journal of the American Chemical Society · OSTI ID:1878521

Chen, Junying; Lee, Yong-Min; Davis, Katherine M.; +8 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Deeper Understanding of Mononuclear Manganese(IV)–Oxo Binding Brønsted and Lewis Acids and the Manganese(IV)–Hydroxide Complex

Citation Formats

References (128)

Linked Research (1)

Similar Records

Related Subjects