Dataset Information

Light-driven, proton-controlled, catalytic aerobic C-H oxidation mediated by a Mn(III) porphyrinoid complex.

ABSTRACT: The visible light-driven, catalytic aerobic oxidation of benzylic C-H bonds was mediated by a Mn(III) corrolazine complex. To achieve catalytic turnovers, a strict selective requirement for the addition of protons was established. The resting state of the catalyst was unambiguously characterized by X-ray diffraction as [Mn(III)(H2O)(TBP8Cz(H))](+), in which a single, remote site on the ligand is protonated. If two remote sites are protonated, however, reactivity with O2 is shut down. Spectroscopic methods revealed that the related Mn(V)(O) complex is also protonated at the same remote site at -60 °C, but undergoes valence tautomerization upon warming.

SUBMITTER: Neu HM

PROVIDER: S-EPMC4888065 | biostudies-literature | 2015 Apr

REPOSITORIES: biostudies-literature

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Light-driven, proton-controlled, catalytic aerobic C-H oxidation mediated by a Mn(III) porphyrinoid complex.

Neu Heather M HM Jung Jieun J Baglia Regina A RA Siegler Maxime A MA Ohkubo Kei K Fukuzumi Shunichi S Goldberg David P DP

Journal of the American Chemical Society 20150403 14

The visible light-driven, catalytic aerobic oxidation of benzylic C-H bonds was mediated by a Mn(III) corrolazine complex. To achieve catalytic turnovers, a strict selective requirement for the addition of protons was established. The resting state of the catalyst was unambiguously characterized by X-ray diffraction as [Mn(III)(H2O)(TBP8Cz(H))](+), in which a single, remote site on the ligand is protonated. If two remote sites are protonated, however, reactivity with O2 is shut down. Spectroscop ...[more]

PMID: 25839905

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Project description:Redox-driven reactions involving Mn(II) species adsorbed at Mn(IV) oxide surfaces can release Mn(III) in the form of dissolved Mn(III)-ligand species in natural waters. Using pyrophosphate (PP) as a model ligand, we show that freezing accelerates and enhances Mn(III) formation in the form of Mn(III)-PP complexes. This freeze-promoted reaction is explained by the concentration of Mn(IV) oxides and solutes (Mn(II), Na+, and Cl-) into the minute fractions of liquid water locked between ice (micro)crystals - the Liquid Intergrain Boundary (LIB). Time-resolved freezing experiments at -20 °C showed that Mn(III) yields were greatest at low salt (NaCl) content. In contrast, high salt content promoted Mn(III) formation through chloride complexation, although yields became lower as the cryosalt mineral hydrohalite (NaCl·2H2O) dehydrated the LIB by drawing water into its structure. Consecutive freeze-thaw cycles also showed that dissolved Mn(III) concentrations increased within the very first few minutes of each freezing event. Because each thaw event released unreacted PP previously locked in ice, each sequential freeze-thaw cycle increased Mn(III) yields, until ∼80% of the Mn was converted to Mn(III). This was achieved after only seven cycles. Finally, temperature-resolved freezing experiments down to -50 °C showed that the LIB produced the greatest quantities of Mn(III) at -10 °C, where the volumes were greater. Reactivity was however sustained in ice formed below the eutectic (-21.3 °C), down to -50 °C. We suspect that this sustained reactivity was driven by persistent forms of supercooled water, such as Mn(IV) oxide-bound thin water films. By demonstrating the freeze-driven production of Mn(III) by comproportionation of dissolved Mn(II) and Mn(IV) oxide, this study highlights the potentially important roles these reactions could play in the production of pools of Mn(III) in natural water and sediments of mid- and high-latitudes environments exposed to freeze-thaw episodes.

Dataset Information

Light-driven, proton-controlled, catalytic aerobic C-H oxidation mediated by a Mn(III) porphyrinoid complex.

Publications

Light-driven, proton-controlled, catalytic aerobic C-H oxidation mediated by a Mn(III) porphyrinoid complex.

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