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Grohsjean, Alexander |
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Falmagne, G. |
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Erice, C. |
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Hernandez, A. M. Vargas |
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Leiton, A. G. Stahl |
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Lipka, K. |
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Pantaleo, F. |
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Torterotot, L. |
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Savina, M. |
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Cerri, O. |
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Jung, A. W. |
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Chiarito, B. |
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Sahin, M. O. |
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Strong, G. |
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Saradhy, R. |
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Joshi, B. M. |
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Kaynak, B. |
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Barrera, C. Baldenegro |
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Longo, Egidio |
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Kolberg, Ted |
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Ferguson, Thomas |
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Leverington, Blake |
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Haase, Fabian |
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Heath, Helen F. |
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Kokkas, Panagiotis |
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Paul, S.
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (16/16 displayed)
- 2022Development of Enzymatic Variants for the Synthesis of Bioresorbable Polyesters
- 2020Impact of Surface Functionalization on the Intrinsic Properties of the Resulting Fe-N-C Catalysts for Fuel Cell Applicationscitations
- 2019Comparative Study of Corrosion Performance of HVOF-Sprayed Coatings Produced Using Conventional and Suspension WC-Co Feedstockcitations
- 2019Influence of silica nanoparticles on corrosion resistance of sol-gel based coatings on mild steelcitations
- 2019A High Spin Mn(IV)-Oxo Complex Generated via Stepwise Proton and Electron Transfer from Mn(III)-Hydroxo Precursor: Characterization and C-H Bond Cleavage Reactivitycitations
- 2019A Comparison of the Potential Capability of SFS, SPS and HVSFS for the Production of Photocatalytic Titania Coatingscitations
- 2019Impact of silica nanoparticles on the morphology and mechanical properties of sol-gel derived coatingscitations
- 2018Performance evaluation of a hard composite solid lubricant coating when dry machining of high-carbon steelcitations
- 2017Influence of silica nanoparticles on corrosion resistance of sol-gel based coatings on mild steel
- 2017Weakly-correlated nature of ferromagnetism in nonsymmorphic CrO%5C(_2%5C) revealed by bulk-sensitive soft-X-ray ARPEScitations
- 2016Antimicrobial, mechanical and thermal studies of silver particle-loaded polyurethane.citations
- 2016Stress analysis in semiconductor devices by Kelvin probe force microscopy
- 2010Materials chemistry for catalysis : Coating of catalytic oxides on metallic foamscitations
- 2007Cryogenic Si detectors for ultra radiation hardness in SLHC environmentcitations
- 2006A steady-state Bi-substrate technique for measurement of the thermal conductivity of ceramic coatings
- 2000Determination of the total $c%5Coverline{c}$ production cross section in 340 GeV/c $%5CSigma^{-}$ - nucleus interactionscitations
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article
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
Abstract
The oxomanganese(IV) complex [(dpaq)Mn-IV (O)](+)-Mn+(1-Mn+ , Mn+ = redox-inactive metal ion, H-dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-ylacetamide), generated in the reaction of the precursor hydroxomanganese(III) complex 1 with iodosylbenzene (PhIO) in the presence of redox-inactive metal triflates, has recently been reported. Herein the generation of the same oxomanganese(IV) species from 1 using various combinations of protic acids and oxidants at 293 K is reported. The reaction of 1 with triflic acid and the one-electron-oxidizing agent [Ru-III (bpy)(3)](3+) leads to the formation of the oxomanganese(IV) complex. The putative species has been identified as a mononuclear high-spin (S = 3/2) nonheme oxomanganese(IV) complex (1-0) on the basis of mass spectrometry, Raman spectroscopy, EPR spectroscopy, and DFT studies. The optical absorption spectrum is well reproduced by theoretical calculations on an S = 3/2 ground spin state of the complex. Isotope labeling studies confirm that the oxygen atom in the oxomanganese(IV) complex originates from the Mn-III - OH precursor and not from water. A mechanistic investigation reveals an initial protonation step forming the Mn-III - OH2 complex, which then undergoes one-electron oxidation and subsequent deprotonations to form the oxomanganese(IV) transient, avoiding the requirements of either oxo-transfer agents or redox-inactive metal ions. The Mn-IV-oxo complex cleaves the C-H bonds of xanthene (k(2) = 5.5 M-1 s(-1)), 9,10-DHA (k(2) = 3.9 M-1 s(-1)), 1,4-CHD (k(2) = 0.25 M-1 s(-1)), and fluorene (k(2) = 0.11 M-1 s(-1)) at 293 K. The electrophilic character of the nonheme Mn-IV-oxo complex is demonstrated by a large negative rho value of 2.5 in the oxidation of para-substituted thioanisoles. The complex emerges as the "most reactive" among the existing Mn-IV/V-oxo complexes bearing anionic ligands.