Ligand Field Effects and the High Spin–High Reactivity Correlation in the H Abstraction by Non-Heme Iron(IV)–Oxo Complexes: A DFT Frontier Orbital Perspective

ACS Catalysis ◽  
2015 ◽  
Vol 5 (3) ◽  
pp. 1475-1488 ◽  
Author(s):  
Andranik Kazaryan ◽  
Evert Jan Baerends
Keyword(s):  
High Spin ◽  
High Reactivity ◽  
Heme Iron ◽  
Ligand Field ◽  
Frontier Orbital ◽  
Oxo Complexes ◽  
Field Effects ◽  
Non Heme Iron

Oxidative Degradation of Toxic Organic Pollutants by Water Soluble Nonheme Iron(IV)-Oxo Complexes of Polydentate Nitrogen Donor Ligands

2021 ◽  
Author(s):  
Sandip Munshi ◽  
Rahul Dev Jana ◽  
Tapan Kanti Paine
Keyword(s):  
Organic Pollutants ◽  
Oxidative Degradation ◽  
Heme Iron ◽  
Water Soluble ◽  
Donor Ligands ◽  
Nitrogen Donor Ligands ◽  
Polydentate Ligands ◽  
Oxo Complexes ◽  
Non Heme Iron ◽  
Nitrogen Donor

The ability of four mononuclear non-heme iron(IV)-oxo complexes supported by nitrogen donor polydentate ligands in degrading organic pollutants has been investigated. The water soluble iron(II) complexes upon treatment with ceric...

scholarly journals Non-heme iron hydroperoxo species in superoxide reductase as a catalyst for oxidation reactions

2014 ◽  
Vol 50 (91) ◽  
pp. 14213-14216 ◽  
Author(s):  
S. Rat ◽  
S. Ménage ◽  
F. Thomas ◽  
V. Nivière
Keyword(s):  
High Spin ◽  
Ferric Iron ◽  
Heme Iron ◽  
Superoxide Reductase ◽  
Oxidation Reactions ◽  
Non Heme Iron

The non-heme high-spin ferric iron hydroperoxo species formed in superoxide reductase can act both as a nucleophile and as an electrophile to catalyze oxidation reactions.

scholarly journals Structure and Reactivity of a High-Spin, Non-Heme Iron(III)-Superoxo Complex Supported by Phosphinimide Ligands

2021 ◽  
Author(s):  
Charles Winslow ◽  
Heui Beom Lee ◽  
Mackenzie J. Field ◽  
Simon J Teat ◽  
Jonathan Rittle
Keyword(s):  
Single Crystals ◽  
High Spin ◽  
Heme Iron ◽  
Computational Studies ◽  
Oxidation Processes ◽  
Transient Nature ◽  
Non Heme Iron ◽  
The Stability ◽  
Oxidation Chemistry ◽  
High Spin Iron

Non-heme iron oxygenases utilize dioxygen to accomplish challenging chemical oxidations. Further understanding of the Fe-O<sub>2</sub> intermediates implicated in these processes is challenged by their highly transient nature. To that end, we have developed a ligand platform featuring phosphinimide donors intended to stabilize oxidized, high-spin iron complexes. O<sub>2</sub> exposure of single crystals of a three-coordinate Fe(II) complex of this framework allowed for in crystallo trapping of a terminally-bound Fe-O<sub>2</sub> complex suitable for XRD characterization. Spectroscopic and computational studies of this species support a high-spin Fe(III) center antiferromagnetically coupled to a superoxide ligand, similar to that proposed for numerous non-heme iron oxygenases. In addition to the stability of this synthetic Fe-O<sub>2</sub> complex, its ability to engage in a range of stoichiometric and catalytic oxidation processes demonstrates that this iron-phosphinimide system is primed for development in modelling oxidizing bioinorganic intermediates and green oxidation chemistry.

Low‐Spin and High‐Spin Perferryl Intermediates in Non‐Heme Iron Catalyzed Oxidations of Aliphatic C–H Groups

2021 ◽  
Author(s):  
Alexandra M. Zima ◽  
Oleg Y. Lyakin ◽  
Konstantin Petrovich Bryliakov ◽  
Evgenii P. Talsi
Keyword(s):  
High Spin ◽  
Heme Iron ◽  
Non Heme Iron

scholarly journals Structure and Reactivity of a High-Spin, Non-Heme Iron(III)-Superoxo Complex Supported by Phosphinimide Ligands

2021 ◽  
Author(s):  
Charles Winslow ◽  
Heui Beom Lee ◽  
Mackenzie J. Field ◽  
Simon J Teat ◽  
Jonathan Rittle
Keyword(s):  
Single Crystals ◽  
High Spin ◽  
Heme Iron ◽  
Computational Studies ◽  
Oxidation Processes ◽  
Transient Nature ◽  
Non Heme Iron ◽  
The Stability ◽  
Oxidation Chemistry ◽  
High Spin Iron

Non-heme iron oxygenases utilize dioxygen to accomplish challenging chemical oxidations. Further understanding of the Fe-O<sub>2</sub> intermediates implicated in these processes is challenged by their highly transient nature. To that end, we have developed a ligand platform featuring phosphinimide donors intended to stabilize oxidized, high-spin iron complexes. O<sub>2</sub> exposure of single crystals of a three-coordinate Fe(II) complex of this framework allowed for in crystallo trapping of a terminally-bound Fe-O<sub>2</sub> complex suitable for XRD characterization. Spectroscopic and computational studies of this species support a high-spin Fe(III) center antiferromagnetically coupled to a superoxide ligand, similar to that proposed for numerous non-heme iron oxygenases. In addition to the stability of this synthetic Fe-O<sub>2</sub> complex, its ability to engage in a range of stoichiometric and catalytic oxidation processes demonstrates that this iron-phosphinimide system is primed for development in modelling oxidizing bioinorganic intermediates and green oxidation chemistry.

Modeling Non-Heme Iron Halogenases: High-Spin Oxoiron(IV)–Halide Complexes That Halogenate C–H Bonds

2016 ◽  
Vol 138 (8) ◽  
pp. 2484-2487 ◽  
Author(s):  
Mayank Puri ◽  
Achintesh N. Biswas ◽  
Ruixi Fan ◽  
Yisong Guo ◽  
Lawrence Que
Keyword(s):  
High Spin ◽  
Heme Iron ◽  
Non Heme Iron ◽  
Halide Complexes
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