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MnIII-Peroxo adduct supported by a new tetradentate ligand shows acid-sensitive aldehyde deformylation reactivity.

ABSTRACT: The new tetradentate L7BQ ligand (L7BQ = 1,4-di(quinoline-8-yl)-1,4-diazepane) has been synthesized and shown to support MnII and MnIII-peroxo complexes. X-ray crystallography of the [MnII(L7BQ)(OTf)2] complex shows a monomeric MnII center with the L7BQ ligand providing four donor nitrogen atoms in the equatorial field, with two triflate ions bound in the axial positions. When this species is treated with H2O2 and Et3N at -40 °C, a MnIII-peroxo adduct, [MnIII(O2)(L7BQ)]+ is formed. The formation of this new intermediate is supported by a variety of spectroscopic techniques, including electronic absorption, Mn K-edge X-ray absorption and electron paramagnetic resonance methods. Evaluation of extended X-ray absorption fine structure data for [MnIII(O2)(L7BQ)]+ resolved Mn-O bond distances of 1.85 Å, which are on the short end of those previously reported for crystallographically characterized MnIII-peroxo adducts. An analysis of the X-ray pre-edge region of [MnIII(O2)(L7BQ)]+ revealed a large pre-edge area of 20.8 units. Time-dependent density functional theory computations indicate that the pre-edge intensity is due to Mn 4p-3d mixing caused by geometric distortions from centrosymmetry induced by both the peroxo and L7BQ ligands. The reactivity of [MnIII(O2)(L7BQ)]+ towards aldehydes was assessed through reaction with cyclohexanecarboxaldehyde and 2-phenylpropionaldehyde. From these experiments, it was determined that [MnIII(O2)(L7BQ)]+ only reacts with aldehydes in the presence of acid. Specifically, the addition of cyclohexanecarboxylic acid to [MnIII(O2)(L7BQ)]+ converts the MnIII-peroxo adduct to a new intermediate that could be responsible for the observed aldehyde deformylation activity. These observations underscore the challenges in identifying the reactive metal species in aldehyde deformylation reactions.

SUBMITTER: Denler MC

PROVIDER: S-EPMC6176719 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

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Mn<sup>III</sup>-Peroxo adduct supported by a new tetradentate ligand shows acid-sensitive aldehyde deformylation reactivity.

Denler Melissa C MC Wijeratne Gayan B GB Rice Derek B DB Colmer Hannah E HE Day Victor W VW Jackson Timothy A TA

Dalton transactions (Cambridge, England : 2003) 20181001 38

The new tetradentate L7BQ ligand (L7BQ = 1,4-di(quinoline-8-yl)-1,4-diazepane) has been synthesized and shown to support MnII and MnIII-peroxo complexes. X-ray crystallography of the [MnII(L7BQ)(OTf)2] complex shows a monomeric MnII center with the L7BQ ligand providing four donor nitrogen atoms in the equatorial field, with two triflate ions bound in the axial positions. When this species is treated with H2O2 and Et3N at -40 °C, a MnIII-peroxo adduct, [MnIII(O2)(L7BQ)]+ is formed. The formation ...[more]

PMID: 30183042

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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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MnIII-Peroxo adduct supported by a new tetradentate ligand shows acid-sensitive aldehyde deformylation reactivity.

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Mn<sup>III</sup>-Peroxo adduct supported by a new tetradentate ligand shows acid-sensitive aldehyde deformylation reactivity.

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