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Activated manganese(IV) oxide can selectively oxidize allylic and benzylic alcohols via a radical intermediate mechanism. Primary allylic alcohols are oxidized to aldehydes, while secondary allylic alcohols yield ketones. The redox reaction of potassium permanganate with an Mn(II) salt such as manganese sulfate (under either alkaline or acidic conditions), followed by thorough drying, yields the oxidizing agent: activated MnO2. While MnO2 is insoluble in the solvents used for the reaction, the...
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In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Metal-Ligand Bonds02:51

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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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Properties of Organometallic Compounds

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Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
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Updated: Jul 9, 2025

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
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Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

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Activated Mn-MACHO Complexes Form Stable CO2 Adducts.

Ajeet Singh1, Gregor Kemper1, Thomas Weyhermüller1

  • 1Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470, Mülheim an der Ruhr, Germany.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|November 30, 2023
PubMed
Summary
This summary is machine-generated.

Manganese complexes with MACHO ligands react with carbon dioxide (CO2) to form metallacycles. These CO2 adducts are less reactive, acting as masked catalysts in CO2 transformations.

Keywords:
carbon dioxide activationhomogeneous catalysismanganese catalystsmetal-ligand cooperativitypincer complexes

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Catalysis

Background:

  • Manganese carbonyl complexes with MACHO ligands are known catalysts.
  • Carbon dioxide (CO2) activation is crucial for sustainable chemistry.
  • Understanding reaction intermediates is key to catalyst design.

Purpose of the Study:

  • To investigate the reaction of manganese(I) amido complexes with CO2.
  • To characterize the resulting metallacycle adducts.
  • To evaluate the reactivity and stability of these adducts.

Main Methods:

  • Synthesis of manganese(I) carbonyl complexes with MACHO ligands.
  • Reaction of amido complexes with CO2.
  • Characterization of the {Mn-N-C-O} metallacycles.
  • Comparative reactivity studies.

Main Results:

  • Formation of stable 4-membered {Mn-N-C-O} metallacycles upon CO2 reaction.
  • Adduct stability inversely correlates with the steric bulk of phosphine substituents (R=isopropyl > adamantyl).
  • CO2 adducts exhibit reduced reactivity compared to parent amido complexes.

Conclusions:

  • The CO2 adducts serve as masked forms of active amido catalysts.
  • These metallacycles may function as off-loop species or branching points in CO2 catalytic cycles.
  • This work provides insights into CO2 fixation mechanisms and catalyst deactivation pathways.