English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Plus monthly

Global: Zendy Tools annual

Global: Zendy Tools monthly

Global: Zendy Free Plan

While alkylperoxomanganese(iii) (Mn III -OOR) intermediates are proposed in the catalytic cycles of several manganese-dependent enzymes, their characterization has proven to be a challenge due to their inherent thermal instability. Fundamental understanding of the structural and electronic properties of these important intermediates is limited to a series of complexes with thiolate-containing N 4 S - ligands. These well-characterized complexes are metastable yet unreactive in the direct oxidation of organic substrates. Because the stability and reactivity of Mn III -OOR complexes are likely to be highly dependent on their local coordination environment, we have generated two new Mn III -OOR complexes using a new amide-containing N 5  - ligand. Using the 2-(bis((6-methylpyridin-2-yl)methyl)amino)- N -(quinolin-8-yl)acetamide (H 6Me dpaq) ligand, we generated the [Mn III (OO  t  Bu)( 6Me dpaq)]OTf and [Mn III (OOCm)( 6Me dpaq)]OTf complexes through reaction of their Mn II or Mn III precursors with  t  BuOOH and CmOOH, respectively. Both of the new Mn III -OOR complexes are stable at room-temperature ( t  1/2 = 5 and 8 days, respectively, at 298 K in CH 3 CN) and capable of reacting directly with phosphine substrates. The stability of these Mn III -OOR adducts render them amenable for detailed characterization, including by X-ray crystallography for [Mn III (OOCm)( 6Me dpaq)]OTf. Thermal decomposition studies support a decay pathway of the Mn III -OOR complexes by O-O bond homolysis. In contrast, direct reaction of [Mn III (OOCm)( 6Me dpaq)] + with PPh 3 provided evidence of heterolytic cleavage of the O-O bond. These studies reveal that both the stability and chemical reactivity of Mn III -OOR complexes can be tuned by the local coordination sphere.

Characterization and chemical reactivity of room-temperature-stable MnIII–alkylperoxo complexes

Characterization and chemical reactivity of room-temperature-stable Mn^III–alkylperoxo complexes