Imperial College London
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Dr Po-Heng (Henry) Lee

Faculty of Engineering, Department of Civil and Environmental Engineering

Senior Lecturer in Wastewater Engineering
 
 
 
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Contact

 

+44 (0)20 7594 5993po-heng.lee

 
 
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Location

 

310ASkempton BuildingSouth Kensington Campus

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Summary

 

Publications

Citation

BibTex format

@article{Wang:2019:10.1039/c9cp00370c,
author = {Wang, J and Zhao, Y-Y and Lee, P-H and Wu, K},
doi = {10.1039/c9cp00370c},
journal = {Phys Chem Chem Phys},
pages = {6643--6650},
title = {Computational analysis of non-heme iron-oxo formation by direct NO release in nitrite reduction.},
url = {http://dx.doi.org/10.1039/c9cp00370c},
volume = {21},
year = {2019}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - A direct NO-releasing reaction of nitrite catalyzed by [N(afaCy)3Fe(OTf)]+ (afa (azafulvene-amine); OTf (trifluoromethanesulfonate); Cy (cyclohexyl)) was investigated using density functional theory (DFT) with D3 dispersion correction. The complex featured a secondary coordination sphere that facilitated the formation of the iron-oxo product [N(afaCy)3FeO]+ with three (Fe)OH-N hydrogen bonds. As a high-spin iron(ii), the O-binding initial intermediate Fe(O)-nitrito was thermodynamically favorable in the S = 2 state. The cleavage of the (Fe)O-NO bond was performed by a β-electron shift to produce Fe(iii)-O by electron rearrangement in the S = 5/2 state. The different electron configurations are responsible for the structural properties, the valence of iron in the complexes, and the pathways of the reactions. Moreover, the two different H-bonds, (Fe)OH-N and (Fe)O-HN (by O-protonation), in the product complexes played a role in determining the reaction channels by impacting the N-H bond rotation. Thus, an exothermic sequence of conversions Fe(ii) → Fe(iii)-O → Fe(iii)-OH → Fe(iii)-O was established for the targeted product formation. This process provided a clue to build two key intermediates, iron-oxo and iron-hydroxo, in a variety of biological and synthetic systems. The results of this study are in agreement with experimental observations and describe the roles of H-bonding in nitrite reduction catalyzed by the non-heme iron complex.
AU  - Wang,J
AU  - Zhao,Y-Y
AU  - Lee,P-H
AU  - Wu,K
DO  - 10.1039/c9cp00370c
EP  - 6650
PY  - 2019///
SP  - 6643
TI  - Computational analysis of non-heme iron-oxo formation by direct NO release in nitrite reduction.
T2  - Phys Chem Chem Phys
UR  - http://dx.doi.org/10.1039/c9cp00370c
UR  - https://www.ncbi.nlm.nih.gov/pubmed/30855607
VL  - 21
ER  -
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