Abstract
A low-valent [FeN5(OTf)2] complex and its bisnitrite adduct, [FeN5(NO2)2], have been synthesized in the interest of extending the reactivity of Fe complexes featuring redox-active ligands with secondary coordination sphere hydrogen-bond donors to nitrite reduction. Crystallographic characterization of [FeN5(NO2)2] reveals that the nitrite ligands demonstrate both ɳ1-NO2 (N-nitro) and ɳ1-ONO (O-nitrito) coordination modes. H-bonding between nitrite ligands and the protons on secondary amine moieties in the N5 ligand play a pivotal role in positioning the nitrite ligands in multiple coordination modes. These results provide insights into the role of H-bonding in supporting disparate coordination modes of this substrate that can be translated to mechanisms of nitrite reduction in biological systems.
Graphical Abstract
Acknowledgement
The authors would like to acknowledge Dr. Banu Kandemir for helpful conversations related to the electrochemistry of the complexes reported in this work.
Disclosure statement
No potential conflict of interest was reported by the authors.