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Catalytic Oxygenation of Hydrocarbons by Mono-μ-oxo Dicopper(II) Species Resulting from O-O Cleavage of Tetranuclear Cu^I /Cu^II Peroxo Complexes.

ABSTRACT: One of the challenges of catalysis is the transformation of inert C-H bonds to useful products. Copper-containing monooxygenases play an important role in this regard. Here we show that low-temperature oxygenation of dinuclear copper(I) complexes leads to unusual tetranuclear, mixed-valent μ₄ -peroxo [Cu^I /Cu^II ]₂ complexes. These Cu₄ O₂ intermediates promote irreversible and thermally activated O-O bond homolysis, generating Cu₂ O complexes that catalyze strongly exergonic H-atom abstraction from hydrocarbons, coupled to O-transfer. The Cu₂ O species can also be produced with N₂ O, demonstrating their capability for small-molecule activation. The binding and cleavage of O₂ leading to the primary Cu₄ O₂ intermediate and the Cu₂ O complexes, respectively, is elucidated with a range of solution spectroscopic methods and mass spectrometry. The unique reactivities of these species establish an unprecedented, 100 % atom-economic scenario for the catalytic, copper-mediated monooxygenation of organic substrates, employing both O-atoms of O₂ .

SUBMITTER: Jurgeleit R

PROVIDER: S-EPMC8251984 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Cuprous and cupric complexes with the new imidazolyl containing tripodal tetradentate ligands {L(MIm), (1H-imidazol-4-yl)-N,N-bis((pyridin-2-yl)methyl)methanamine, and L(EIm), 2-(1H-imidazol-4-yl)-N,N-bis((pyridin-2-yl)methyl)ethanamine}, have been investigated to probe differences in their chemistry, especially in copper(I)-dioxygen chemistry, compared to that already known for the pyridyl analogue TMPA, tris(2-pyridyl)methyl)amine. Infrared (IR) stretching frequencies obtained from carbon monoxide adducts of [(L(MIm))Cu(I)](+) (1a) and [(L(EIm))Cu(I)](+) (2a) show that the imidazolyl donor is stronger than its pyridyl analogue. Electrochemical data suggest differences in the binding constant of Cu(II) to L(EIm) compared to TMPA and L(MIm), reflecting geometric changes. Oxygenation of [(L(MIm))Cu(I)](+) (1a) in 2-methyltetrahydrofuran (MeTHF) solvent at -128 degrees C leads to an intensely purple colored species with a UV-vis spectrum characteristic of an end-on bound peroxodicopper(II) complex [{(L(MIm))Cu(II)}(2)(mu-1,2-O(2)(2-))](2+) (1b(P)) {lambda(max) = 528 nm}, very similar to the previously well characterized complex [{(TMPA)Cu(II)}(2)(mu-1,2-O(2)(2-))](2+) {lambda(max) = 520 nm (epsilon = 12 000 M(-1) cm(-1)), in MeTHF; resonance Raman (rR) spectroscopy: nu(O-O) = 832 (Delta((18)O(2)) = -44) cm(-1)}. In the low-temperature oxygenation of 2a, benchtop (-128 degrees C) and stopped-flow (-90 degrees C) experiments reveal the formation of an initial superoxo-Cu(II) species [(L(EIm))Cu(II)(O(2)(*-))](+) (2b(S)), lambda(max) = 431 nm in THF) . This converts to the low-temperature stable peroxo complex [{(L(EIm))Cu(II)}(2)(mu-1,2-O(2)(2-))](2+) (2b(P)) {rR spectroscopy: nu(O-O) = 822 (Delta((18)O(2)) = -46) cm(-1)}. Complex 2b(P) possess distinctly reduced Cu-O and O-O stretching frequencies and a red-shifted UV-vis feature {to lambda(max) = 535 nm (epsilon = 11 000 M(-1) cm(-1))} compared to the TMPA analogue due to a distortion from trigonal bipyramidal (TBP) to a square pyramidal ligand field. This distortion is supported by the structural characterization of related ligand-copper(II) complexes: A stable tetramer cluster complex [(mu(2)-L(EIm-))(4)(Cu(II))(4)](4+), obtained from thermal decomposition of 2b(P) (with formation of H(2)O(2)), also exhibits a distorted square pyramidal Cu(II) ion geometry as does the copper(II) complex [(L(EIm))Cu(II)(CH(3)CN)](2+) (2c), characterized by X-ray crystallography and solution electron paramagnetic resonance (EPR) spectroscopy.

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Catalytic Oxygenation of Hydrocarbons by Mono-μ-oxo Dicopper(II) Species Resulting from O-O Cleavage of Tetranuclear Cu^I /Cu^II Peroxo Complexes.

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Catalytic Oxygenation of Hydrocarbons by Mono-μ-oxo Dicopper(II) Species Resulting from O-O Cleavage of Tetranuclear CuI /CuII Peroxo Complexes.

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OmicsDI is part of the ELIXIR infrastructure

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Catalytic Oxygenation of Hydrocarbons by Mono-μ-oxo Dicopper(II) Species Resulting from O-O Cleavage of Tetranuclear Cu^I /Cu^II Peroxo Complexes.