ArticleDalton transactions (Cambridge, England : 2003)2018
Mn
Article in Dalton transactions (Cambridge, England : 2003), 2018. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 2 papers.
What it found
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The abstract states no effect estimate the extractor could read, or names no intervention and outcome on the map, so this paper lights no cell and moves no belief. It is still indexed, cited and linked below.
The trial behind it
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Who cites it
2 citing papers in PubMed.
- Mechanistic Divergence in Sulfur-Ligated Iron(III)-Alkylperoxo Reactivity: Aldehyde Oxidation Prevails over Deformylation.Angewandte Chemie (International ed. in English) · 2025Article
- Dioxygenase Chemistry in Nucleophilic Aldehyde Deformylations Utilizing Dicopper OJournal of the American Chemical Society · 2024Article
Corrections and comments
PubMed lists nothing against this paper. Absence here is not a guarantee, only a check that was made.
Authors and funding
6 authors.
Funding
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.
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Registered trials
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