Mn IV -oxo Complex of a Bis(benzimidazolyl)-containing N5 Ligand Reveals Different Reactivity Trends for Mn IV -oxo than Fe IV -oxo Species

Using the pentadentate ligand (N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine, 2pyN2B), presenting two pyridyl and two (N-methyl)benzimidazolyl donor moieties in addition to a central tertiary amine, new Mn II and Mn IV -oxo complexes were generated and characterized. The [Mn IV (O)(2pyN2B)] 2+ complex showed spectroscopic signatures (i.e., electronic absorption band maxima and intensities, EPR signals, and Mn K-edge X-ray absorption edge and near-edge data) similar to those observed for other Mn IV -oxo complexes with neutral, pentadentate N 5 supporting ligands. The near-IR electronic absorption band maximum of [Mn IV (O)(2pyN2B)] 2+ , as well as DFT-computed metric parameters, are consistent with the equatorial (N-methyl)benzimidazolyl ligands being stronger donors to the Mn IV center than the pyridyl and quinolinyl ligands found in analogous Mn IV -oxo complexes. The hydrogen- and oxygen-atom transfer reactivities of [Mn IV (O)(2pyN2B)] 2+ were assessed through reactions with hydrocarbons and thioanisole, respectively. When compared with related Mn IV -oxo adducts, [Mn IV (O)(2pyN2B)]

[1]  Timothy A. Jackson,et al.  Ligand Influence on Structural Properties and Reactivity of Bis(μ-oxo)dimanganese(III,IV) Species and Comparison of Reactivity with Terminal MnIV -oxo Complexes , 2018, ChemistrySelect.

[2]  S. Fukuzumi,et al.  Hydrogen Atom Transfer Reactions of Mononuclear Nonheme Metal-Oxygen Intermediates. , 2018, Accounts of chemical research.

[3]  M. Costas,et al.  The Quest for Selectivity in Hydrogen Atom Transfer Based Aliphatic C-H Bond Oxygenation. , 2018, Accounts of chemical research.

[4]  Timothy A. Jackson,et al.  Relationship between Hydrogen-Atom Transfer Driving Force and Reaction Rates for an Oxomanganese(IV) Adduct. , 2018, Inorganic chemistry.

[5]  Saikat Banerjee,et al.  Crystallographic Evidence for a Sterically Induced Ferryl Tilt in a Non-Heme Oxoiron(IV) Complex that Makes it a Better Oxidant. , 2018, Angewandte Chemie.

[6]  Timothy A. Jackson,et al.  Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions. , 2017, Accounts of chemical research.

[7]  I. Leito,et al.  On the Basicity of Conjugated Nitrogen Heterocycles in Different Media , 2017 .

[8]  Timothy A. Jackson,et al.  Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)-Oxo Complexes. , 2017, Angewandte Chemie.

[9]  Timothy A. Jackson,et al.  Spectroscopic and Computational Investigations of a Mononuclear Manganese(IV)-Oxo Complex Reveal Electronic Structure Contributions to Reactivity. , 2016, Journal of the American Chemical Society.

[10]  Timothy A. Jackson,et al.  X-Band Electron Paramagnetic Resonance Comparison of Mononuclear Mn(IV)-oxo and Mn(IV)-hydroxo Complexes and Quantum Chemical Investigation of Mn(IV) Zero-Field Splitting. , 2016, Inorganic chemistry.

[11]  D. Maiti,et al.  Mechanistic elucidation of C-H oxidation by electron rich non-heme iron(IV)-oxo at room temperature. , 2015, Chemical communications.

[12]  Williamson N. Oloo,et al.  Bioinspired Nonheme Iron Catalysts for C-H and C═C Bond Oxidation: Insights into the Nature of the Metal-Based Oxidants. , 2015, Accounts of chemical research.

[13]  Junying Chen,et al.  Mononuclear nonheme iron(IV)-oxo and manganese(IV)-oxo complexes in oxidation reactions: experimental results prove theoretical prediction. , 2015, Chemical communications.

[14]  W. Browne,et al.  Nonheme Fe(IV) Oxo Complexes of Two New Pentadentate Ligands and Their Hydrogen-Atom and Oxygen-Atom Transfer Reactions. , 2015, Inorganic chemistry.

[15]  L. Que,et al.  Toward the Synthesis of More Reactive S = 2 Non-Heme Oxoiron(IV) Complexes , 2015, Accounts of chemical research.

[16]  P. Comba,et al.  Influence of ligand architecture on oxidation reactions by high-valent nonheme manganese oxo complexes using water as a source of oxygen. , 2015, Angewandte Chemie.

[17]  Timothy A. Jackson,et al.  Saturation kinetics in phenolic O-H bond oxidation by a mononuclear Mn(III)-OH complex derived from dioxygen. , 2014, Inorganic chemistry.

[18]  Timothy A. Jackson,et al.  Spectroscopic properties and reactivity of a mononuclear oxomanganese(IV) complex. , 2013, Chemical communications.

[19]  S. Shaik,et al.  Theoretical Investigations into C–H Bond Activation Reaction by Nonheme MnIVO Complexes: Multistate Reactivity with No Oxygen Rebound , 2012 .

[20]  Junying Chen,et al.  A highly reactive mononuclear non-heme manganese(IV)-oxo complex that can activate the strong C-H bonds of alkanes. , 2011, Journal of the American Chemical Society.

[21]  P. Comba,et al.  A combined experimental and computational study on the sulfoxidation by high-valent iron bispidine complexes. , 2011, Dalton transactions.

[22]  J. Mayer,et al.  Thermochemistry of proton-coupled electron transfer reagents and its implications. , 2010, Chemical reviews.

[23]  S. Shaik,et al.  Water as an oxygen source: synthesis, characterization, and reactivity studies of a mononuclear nonheme manganese(IV) oxo complex. , 2010, Angewandte Chemie.

[24]  Marcin Wojdyr,et al.  Fityk: a general-purpose peak fitting program , 2010 .

[25]  Martin Maurer,et al.  Oxidation of cyclohexane by high-valent iron bispidine complexes: tetradentate versus pentadentate ligands. , 2009, Inorganic chemistry.

[26]  C. Cramer,et al.  Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. , 2009, The journal of physical chemistry. B.

[27]  A. Borovik,et al.  C-H bond cleavage with reductants: re-investigating the reactivity of monomeric Mn(III/IV)-oxo complexes and the role of oxo ligand basicity. , 2009, Journal of the American Chemical Society.

[28]  Youngmee Kim,et al.  [Mn(tmc)(O2)]+: a side-on peroxido manganese(III) complex bearing a non-heme ligand. , 2007, Angewandte Chemie.

[29]  P. Comba,et al.  Catalytic epoxidation and 1,2-dihydroxylation of olefins with bispidine-iron(II)/H2O2 systems. , 2006, Angewandte Chemie.

[30]  F. Weigend,et al.  Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. , 2005, Physical chemistry chemical physics : PCCP.

[31]  M Newville,et al.  ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. , 2005, Journal of synchrotron radiation.

[32]  L. Que,et al.  Nonheme FeIVO complexes that can oxidize the C-H bonds of cyclohexane at room temperature. , 2004, Journal of the American Chemical Society.

[33]  G. Scuseria,et al.  Climbing the density functional ladder: nonempirical meta-generalized gradient approximation designed for molecules and solids. , 2003, Physical review letters.

[34]  E. C. Wilkinson,et al.  NONHEME IRON CENTERS IN OXYGEN ACTIVATION : CHARACTERIZATION OF AN IRON(III) HYDROPEROXIDE INTERMEDIATE , 1995 .

[35]  A. Schäfer,et al.  Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr , 1994 .

[36]  Hans W. Horn,et al.  Fully optimized contracted Gaussian basis sets for atoms Li to Kr , 1992 .

[37]  Frank Neese,et al.  The ORCA program system , 2012 .

[38]  D. D. Perrin,et al.  Purification of Laboratory Chemicals , 2022 .