Mechanistic insight into the hydroxylation of alkanes by a nonheme iron(v)–oxo complex

2014 ◽  
Vol 50 (42) ◽  
pp. 5572-5575 ◽  
Author(s):  
Eunji Kwon ◽  
Kyung-Bin Cho ◽  
Seungwoo Hong ◽  
Wonwoo Nam
Keyword(s):  
Hydrogen Atom ◽  
Nonheme Iron ◽  
Hydrogen Atom Abstraction ◽  
Alkane Hydroxylation ◽  
Mechanistic Insight ◽  
Insight Into

The alkane hydroxylation by a mononuclear nonheme iron(v)–oxo complex occurs via a hydrogen-atom abstraction–oxygen non-rebound mechanism.

Properties and reactivities of nonheme iron(iv)–oxo versus iron(v)–oxo: long-range electron transfer versus hydrogen atom abstraction

2014 ◽  
Vol 16 (41) ◽  
pp. 22611-22622 ◽  
Author(s):  
Baharan Karamzadeh ◽  
Devendra Singh ◽  
Wonwoo Nam ◽  
Devesh Kumar ◽  
Sam P. de Visser
Keyword(s):  
Electron Transfer ◽  
Hydrogen Atom ◽  
Long Range ◽  
Cation Radical ◽  
Nonheme Iron ◽  
Hydrogen Atom Abstraction ◽  
Computational Studies ◽  
Radical Species ◽  
Oxo Ligand

Computational studies show that the perceived nonheme iron(v)–oxo is actually an iron(iv)–oxo ligand cation radical species.

Structural and mechanistic insight into alkane hydroxylation by Pseudomonas putida AlkB

2014 ◽  
Vol 460 (2) ◽  
pp. 283-293 ◽  
Author(s):  
Hernan Alonso ◽  
Oded Kleifeld ◽  
Adva Yeheskel ◽  
Poh C. Ong ◽  
Yu C. Liu ◽  
...  
Keyword(s):  
Ab Initio ◽  
Pseudomonas Putida ◽  
Structure And Function ◽  
Alkane Hydroxylation ◽  
Mechanistic Insight ◽  
Unknown Structure ◽  
And Function ◽  
Alkane Hydroxylases ◽  
Insight Into

Integral membrane non-haem di-iron alkane hydroxylases (AlkBs) are enzymes of unknown structure that allow bacteria to grow on alkanes. Catalysis-linked modifications with the inhibitor 1-octyne, mutagenesis studies and ab initio modelling provided novel insights into the structure and function of AlkB.

Mechanistic Insight into the Nitric Oxide Dioxygenation Reaction of Nonheme Iron(III)-Superoxo and Manganese(IV)-Peroxo Complexes

2016 ◽  
Vol 128 (40) ◽  
pp. 12591-12595 ◽  
Author(s):  
Seungwoo Hong ◽  
Pankaj Kumar ◽  
Kyung-Bin Cho ◽  
Yong-Min Lee ◽  
Kenneth D. Karlin ◽  
...  
Keyword(s):  
Nitric Oxide ◽  
Nonheme Iron ◽  
Peroxo Complexes ◽  
Mechanistic Insight ◽  
Insight Into

scholarly journals Formation and characterization of a reactive chromium(v)–oxo complex: mechanistic insight into hydrogen-atom transfer reactions

2015 ◽  
Vol 6 (2) ◽  
pp. 945-955 ◽  
Author(s):  
Hiroaki Kotani ◽  
Suzue Kaida ◽  
Tomoya Ishizuka ◽  
Miyuki Sakaguchi ◽  
Takashi Ogura ◽  
...  
Keyword(s):  
Hydrogen Atom ◽  
Reaction Mechanisms ◽  
Hydrogen Atom Transfer ◽  
Transfer Reactions ◽  
Atom Transfer ◽  
Oxidation Potentials ◽  
Mechanistic Insight ◽  
Atom Transfer Reactions ◽  
Insight Into

Mechanistic insights were gained into hydrogen-atom transfer reactions from benzyl alcohol derivatives with different oxidation potentials to a highly reactive Cr(v)–oxo complex to reveal switching of reaction mechanisms.

scholarly journals Mechanistic Insight into the Nitric Oxide Dioxygenation Reaction of Nonheme Iron(III)-Superoxo and Manganese(IV)-Peroxo Complexes

2016 ◽  
Vol 55 (40) ◽  
pp. 12403-12407 ◽  
Author(s):  
Seungwoo Hong ◽  
Pankaj Kumar ◽  
Kyung-Bin Cho ◽  
Yong-Min Lee ◽  
Kenneth D. Karlin ◽  
...  
Keyword(s):  
Nitric Oxide ◽  
Nonheme Iron ◽  
Peroxo Complexes ◽  
Mechanistic Insight ◽  
Insight Into

scholarly journals Density Functional Theory Study into the Reaction Mechanism of Isonitrile Biosynthesis by the Nonheme Iron Enzyme ScoE

2021 ◽  
Author(s):  
Hafiz Saqib Ali ◽  
Sidra Ghafoor ◽  
Sam P. de Visser
Keyword(s):  
Reaction Mechanism ◽  
Hydrogen Atom ◽  
Proton Transfer ◽  
Active Site ◽  
Density Functional ◽  
Active Species ◽  
Nonheme Iron ◽  
Catalytic Cycle ◽  
Hydrogen Atom Abstraction ◽  
Catalytic Cycles

AbstractThe nonheme iron enzyme ScoE catalyzes the biosynthesis of an isonitrile substituent in a peptide chain. To understand details of the reaction mechanism we created a large active site cluster model of 212 atoms that contains substrate, the active oxidant and the first- and second-coordination sphere of the protein and solvent. Several possible reaction mechanisms were tested and it is shown that isonitrile can only be formed through two consecutive catalytic cycles that both use one molecule of dioxygen and α-ketoglutarate. In both cycles the active species is an iron(IV)-oxo species that in the first reaction cycle reacts through two consecutive hydrogen atom abstraction steps: first from the N–H group and thereafter from the C–H group to desaturate the NH-CH2 bond. The alternative ordering of hydrogen atom abstraction steps was also tested but found to be higher in energy. Moreover, the electronic configurations along that pathway implicate an initial hydride transfer followed by proton transfer. We highlight an active site Lys residue that is shown to donate charge in the transition states and influences the relative barrier heights and bifurcation pathways. A second catalytic cycle of the reaction of iron(IV)-oxo with desaturated substrate starts with hydrogen atom abstraction followed by decarboxylation to give isonitrile directly. The catalytic cycle is completed with a proton transfer to iron(II)-hydroxo to generate the iron(II)-water resting state. The work is compared with experimental observation and previous computational studies on this system and put in a larger perspective of nonheme iron chemistry.

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