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

Journal Article · · Inorganic Chemistry
 [1];  [2];  [3];  [4];  [1]
  1. The Johns Hopkins Univ., Baltimore, MD (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. The Johns Hopkins Univ., Baltimore, MD (United States); Univ. of Wisconsin, Madison, WI (United States)
  4. The Johns Hopkins Univ., Baltimore, MD (United States); Chulalongkorn Univ., Bangkok (Thailand)
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The addition of Lewis or Brönsted acids (LA = Zn(OTf)2, B(C6F5)3, HBArF, TFA) to the high-valent manganese–oxo complex MnV(O)(TBP8Cz) results in the stabilization of a valence tautomer MnIV(O-LA)(TBP8Cz•+). The ZnII and B(C6F5)3 complexes were characterized by manganese K-edge X-ray absorption spectroscopy (XAS). The position of the edge energies and the intensities of the pre-edge (1s to 3d) peaks confirm that the Mn ion is in the +4 oxidation state. Fitting of the extended X-ray absorption fine structure (EXAFS) region reveals 4 N/O ligands at Mn–Nave = 1.89 Å and a fifth N/O ligand at 1.61 Å, corresponding to the terminal oxo ligand. This Mn–O bond length is elongated compared to the MnV(O) starting material (Mn–O = 1.55 Å). The reactivity of MnIV(O-LA)(TBP8Cz•+) toward C–H substrates was examined, and it was found that H• abstraction from C–H bonds occurs in a 1:1 stoichiometry, giving a MnIV complex and the dehydrogenated organic product. The rates of C–H cleavage are accelerated for the MnIV(O-LA)(TBP8Cz•+) valence tautomer as compared to the MnV(O) valence tautomer when LA = ZnII, B(C6F5)3, and HBArF, whereas for LA = TFA, the C–H cleavage rate is slightly slower than when compared to MnV(O). A large, nonclassical kinetic isotope effect of kH/kD = 25–27 was observed for LA = B(C6F5)3 and HBArF, indicating that H-atom transfer (HAT) is the rate-limiting step in the C–H cleavage reaction and implicating a potential tunneling mechanism for HAT. Furthermore, the reactivity of MnIV(O-LA)(TBP8Cz•+) toward C–H bonds depends on the strength of the Lewis acid. The HAT reactivity is compared with the analogous corrole complex MnIV(O–H)(tpfc•+) recently reported.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
GM101153; AC02-76SF00515
OSTI ID:
1350592
Journal Information:
Inorganic Chemistry, Vol. 55, Issue 20; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 41 works
Citation information provided by
Web of Science

References (67)

Cytochrome P450 Compound I: Capture, Characterization, and C-H Bond Activation Kinetics journal November 2010
Structure and Chemistry of Cytochrome P450 journal June 2005
Heme Enzyme Structure and Function journal January 2014
Valence-tautomerism in high-valent iron and manganese porphyrins journal October 2001
Valence Tautomerism: New Challenges for Electroactive Ligands journal August 2005
Preface: Forum on Redox-Active Ligands journal October 2011
Valence Tautomerism in a High-Valent Manganese–Oxo Porphyrinoid Complex Induced by a Lewis Acid journal June 2012
Activation of a High-Valent Manganese–Oxo Complex by a Nonmetallic Lewis Acid journal May 2014
Strong Inhibition of O-Atom Transfer Reactivity for Mn IV (O)(π-Radical-Cation)(Lewis Acid) versus Mn V (O) Porphyrinoid Complexes journal May 2015
Light-Driven, Proton-Controlled, Catalytic Aerobic C–H Oxidation Mediated by a Mn(III) Porphyrinoid Complex journal April 2015
Formation of Iron(III) meso -Chloro-isoporphyrin as a Reactive Chlorinating Agent from Oxoiron(IV) Porphyrin π-Cation Radical journal March 2012
Ferryl Protonation in Oxoiron(IV) Porphyrins and Its Role in Oxygen Transfer journal February 2015
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 journal March 2008
Valence Tautomerization of High-Valent Manganese(V)-Oxo Corrole Induced by Protonation of the Oxo Ligand journal November 2015
Crystal structure of oxygen-evolving photosystem II at a resolution of 1.9 Å journal April 2011
Redox-inactive metals modulate the reduction potential in heterometallic manganese–oxido clusters journal March 2013
Native structure of photosystem II at 1.95 Å resolution viewed by femtosecond X-ray pulses journal November 2014
Unified View of Oxidative C–H Bond Cleavage and Sulfoxidation by a Nonheme Iron(IV)–Oxo Complex via Lewis Acid-Promoted Electron Transfer journal March 2014
A Mononuclear Non-Heme Manganese(IV)–Oxo Complex Binding Redox-Inactive Metal Ions journal January 2013
Tuning the reactivity of mononuclear nonheme manganese( iv )-oxo complexes by triflic acid journal January 2015
Lewis-Acid-Promoted Stoichiometric and Catalytic Oxidations by Manganese Complexes Having Cross-Bridged Cyclam Ligand: A Comprehensive Study journal April 2013
BF 3 -Activated Oxidation of Alkanes by MnO 4 - journal February 2006
Molecular Designs for Controlling the Local Environments around Metal Ions journal July 2015
Synthesis, Characterization, and Physicochemical Properties of Manganese(III) and Manganese(V)−Oxo Corrolazines journal June 2005
Dramatic Influence of an Anionic Donor on the Oxygen-Atom Transfer Reactivity of a Mn V -Oxo Complex journal September 2014
Characterization of an Oxo(porphyrinato)manganese(IV) Complex by X-ray Absorption Spectroscopy journal February 1995
Spectroscopic properties and reactivity of a mononuclear oxomanganese(iv) complex journal January 2013
Mn(V)(O) versus Cr(V)(O) Porphyrinoid Complexes: Structural Characterization and Implications for Basicity Controlling H-Atom Abstraction journal August 2015
The Electronic Nature of Terminal Oxo Ligands in Transition-Metal Complexes: Ambiphilic Reactivity of Oxorhenium Species journal June 2013
Enhanced Electron-Transfer Reactivity of Nonheme Manganese(IV)–Oxo Complexes by Binding Scandium Ions journal June 2013
Z-Selective Olefin Metathesis Reactions Promoted by Tungsten Oxo Alkylidene Complexes
  • Peryshkov, Dmitry V.; Schrock, Richard R.; Takase, Michael K.
  • Journal of the American Chemical Society, Vol. 133, Issue 51, p. 20754-20757 https://doi.org/10.1021/ja210349m
journal December 2011
Adducts of the Lewis acid [B(C6F5)3] with transition metal oxo compounds journal January 1999
Oxygen-Bridged Iron-Copper Assemblies Pertinent to Heme-Copper Oxidases: Synthesis and Structure of an [FeIII-(OH)-CuII] Bridge and Exafs Multiple-Scattering Effects of Linear Oxo and Nonlinear Hydroxo Bridges journal January 1995
XAS Structural Comparisons of Reversibly Interconvertible Oxo- and Hydroxo-Bridged Heme-Copper Oxidase Model Compounds journal January 1996
Electronic Structure and Reactivity of Isomeric Oxo-Mn(V) Porphyrins:  Effects of Spin-State Crossing and p K a Modulation journal May 2006
What Is the Difference between the Manganese Porphyrin and Corrole Analogues of Cytochrome P450's Compound I? journal November 2001
Manganese Oxyl Radical Intermediates and O−O Bond Formation in Photosynthetic Oxygen Evolution and a Proposed Role for the Calcium Cofactor in Photosystem II journal January 1999
Manganese Nitride Complexes in Oxidation States III, IV, and V: Synthesis and Electronic Structure journal September 2012
A low spin manganese( iv ) nitride single molecule magnet journal January 2016
Electron- and Hydride-Transfer Reactivity of an Isolable Manganese(V)−Oxo Complex journal February 2011
Hydrogen Atom Abstraction by a High-Valent Manganese(V)−Oxo Corrolazine journal May 2006
The Influence of Peripheral Substituent Modification on P V , Mn III , and Mn V (O) Corrolazines: X-ray Crystallography, Electrochemical and Spectroscopic Properties, and HAT and OAT Reactivities journal August 2016
The acceptor number ? A quantitative empirical parameter for the electrophilic properties of solvents journal January 1975
A convenient n.m.r. method for the measurement of Lewis acidity at boron centres: correlation of reaction rates of Lewis acid initiated epoxide polymerizations with Lewis acidity journal September 1996
Unprecedented Rate Enhancements of Hydrogen-Atom Transfer to a Manganese(V)-Oxo Corrolazine Complex journal June 2010
Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications journal December 2010
Understanding Hydrogen Atom Transfer: From Bond Strengths to Marcus Theory journal January 2011
A High-Valent Iron–Oxo Corrolazine Activates C–H Bonds via Hydrogen-Atom Transfer journal April 2012
Switchover of the Mechanism between Electron Transfer and Hydrogen-Atom Transfer for a Protonated Manganese(IV)-Oxo Complex by Changing Only the Reaction Temperature journal May 2016
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 journal March 2013
Synthesis, Crystal Structure, and Application of the Oxonium Acid [H(OEt 2 ) 2 ] + [B(C 6 F 5 ) 4 ] - journal April 2000
C−H Bond Activation by a Ferric Methoxide Complex:  Modeling the Rate-Determining Step in the Mechanism of Lipoxygenase journal January 2002
The ORCA program system: The ORCA program system journal June 2011
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals journal January 1985
Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg journal January 1985
The role of databases in support of computational chemistry calculations journal October 1996
Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi journal January 1985
Basis Set Exchange:  A Community Database for Computational Sciences journal March 2007
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules journal March 1972
Molecular density functional calculations in the regular relativistic approximation: Method, application to coinage metal diatomics, hydrides, fluorides and chlorides, and comparison with first-order relativistic calculations journal July 1998
All-Electron Scalar Relativistic Basis Sets for Third-Row Transition Metal Atoms journal May 2008
Density-functional approximation for the correlation energy of the inhomogeneous electron gas journal June 1986
Density-functional exchange-energy approximation with correct asymptotic behavior journal September 1988
Energy‐adjusted a b i n i t i o pseudopotentials for the first row transition elements journal January 1987
Generalized Gradient Approximation Made Simple journal October 1996

Cited By (8)

Synthetic High-Valent M-O-X Oxidants: Synthetic High-Valent M-O-X Oxidants journal January 2018
meso-N-Methylation of a porphyrinoid complex: activating the H-atom transfer capability of an inert Re V (O) corrolazine journal January 2017
C–H activation and nucleophilic substitution in a photochemically generated high valent iron complex journal January 2018
A High‐Valent Manganese(IV)–Oxo–Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity journal November 2019
A Manganese(V)–Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies journal November 2018
A High‐Valent Manganese(IV)–Oxo–Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity journal September 2019
Interaction of Metal Oxido Compounds with B(C 6 F 5 ) 3 journal February 2019
Effects of Hypertension and Hypercarbia on Spinal Cord Tissue Oxygen in Acute Experimental Spinal Cord Injury journal June 1980

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