The most reactive iron and manganese complexes with N-pentadentate ligands for dioxygen activation—synthesis, characteristics, applications

  title={The most reactive iron and manganese complexes with N-pentadentate ligands for dioxygen activation—synthesis, characteristics, applications},
  author={Katarzyna Rydel-Ciszek},
  journal={Reaction Kinetics, Mechanisms and Catalysis},
  pages={579 - 600}
The iron and manganese complexes that activate oxygen atom play multiple role in technologically relevant reactions as well as in biological transformations, in which exist in different redox states. Among them, high-valent oxo intermediate seems to be the most important one. Iron, and/or manganese-based processes have found application in many areas, starting from catalysis and sustainable technologies, through DNA oxidative cleavage, to new substances useful in chemotherapeutic drugs. This… 


Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective.
Analysis of recent examples of biomimetic Fe and Mn complexes that exhibit reactivity with O2 and lead to spectroscopically observable metal-oxygen species, and/or oxidize biologically relevant substrates reveals that solvent, spin state, redox potential, external co-reductants, and ligand architecture can all play important roles in the O2 activation process.
Dioxygen activation by mononuclear nonheme iron(II) complexes generates iron-oxygen intermediates in the presence of an NADH analogue and proton.
The first example of generating nonheme iron(III)-hydroperoxo and iron(IV)-oxo complexes by activating O(2) with a biologically important electron donor, an NADH analogue, and an acid is reported.
The biology and chemistry of high-valent iron-oxo and iron-nitrido complexes.
Advances in the chemistry of model high-valent iron-oxo and -nitrido systems can be related to the understanding of the biological systems and can provide vital insights into the mechanism of such enzymatic reactions.
Sluggish reactivity by a nonheme iron(iv)-tosylimido complex as compared to its oxo analogue.
It is shown that the reactivity of iron(iv)-imido complexes is dependent on the metal ligand system that affects the physicochemical properties of the oxidant such as the redox potential, which is the main driving force for the reaction mechanism with substrates.
Importance of Metal-Ion Exchange for the Biological Activity of Coordination Complexes of the Biomimetic Ligand N4Py
This study shows that a mixture of iron(II), copper(II, and zinc(II) complexes can be generated when N4Py is added to cell cultures but that the metal ion can also be exchanged by other metal ions present in cells.
Involvement of high-valent manganese-oxo intermediates in oxidation reactions: realisation in nature, nano and molecular systems
Recent advances and key lessons learned from the nature on high-valent Mn-oxo intermediates are described and how the novel strategies are realised in nano particles and molecular sites at heterogeneous and homogeneous reaction conditions respectively are proposed.
A mononuclear non-heme manganese(IV)-oxo complex binding redox-inactive metal ions.
The present results provide the first example of a non-heme Mn(IV)-oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox -in active metal ions on the reactivities of metal-oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.
High-Valent Nonheme Iron Oxidants in Biology: Lessons from Synthetic FeIV=O Complexes.
  • L. Que
  • Chemistry, Biology
    Bulletin of Japan Society of Coordination Chemistry
  • 2013
It is conjectured that O2 binding to the metal center initiates a reaction sequence that leads to the cleavage of the O–O bond and formation of a high-valent metal-oxo species responsible for C–H bond functionalization.