RT info:eu-repo/semantics/article
T1 Secondary Coordination Sphere Influences the Formation of Fe(III)-O or Fe(III)-OH in Nitrite Reduction: A Synthetic and Computational Study
A1 Park, Yun Ji
A1 Drummond, Michael J.
A1 Gordon, Zachary
A1 Kelly, Oscar R.
A1 Garvey, Ian J.
A1 Gullett, Kelly L.
A1 García Melchor, Max
A1 Fout, Alison R.
A1 Peñas de Frutos, Marconi Nicolás
K1 Química Organometálica
AB The reduction of nitrite (NO2–) to generate nitric oxide (NO) is a significant area of research due to their roles in the global nitrogen cycle. Here we describe various modifications of the tris(5-cyclohexyliminopyrrol-2-ylmethyl)amine H3[N(piR)3] ligand where the steric bulk and acidity of the secondary coordination sphere were explored in the non-heme iron system for nitrite reduction. The cyclohexyl and 2,4,6-trimethylphenyl variants of the ligand were used to probe the mechanismof nitrite reduction. While previously stoichiometric addition of nitrite to the iron(II)-species generated an iron(III)-oxo complex, changing the secondary coordination sphere to mesityl resulted in an iron(III) hydroxo complex. Subsequent addition of an electron and two protons led to the release of water and regeneration of the starting iron(II) catalyst. This sequence mirrored the proposed mechanism of nitrite reduction in biological systems, where the distal histidine residue shuttles protons to the active site. Computational studies aimed at interrogating the dissimilar behavior of the cyclohexyl and mesityl ligand systems resulting in Fe(III)-oxo and Fe(III)-hydroxo complexes, respectively, shed light on the key role of H-bonds involving the secondary coordination sphere on the relative stability of these species.
PB American Chemical Society
SN 0020-1669
YR 2022
FD 2022
LK https://uvadoc.uva.es/handle/10324/75097
UL https://uvadoc.uva.es/handle/10324/75097
LA spa
NO Inorg. Chem. 2022, 61, 8182
NO Producción Científica
DS UVaDOC
RD 22-feb-2025