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A Triad of Highly Reduced, Linear Iron Nitrosyl Complexes: {FeNO} 8–10
Author(s) -
Chalkley Matthew J.,
Peters Jonas C.
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201605403
Subject(s) - chemistry , electron paramagnetic resonance , redox , borane , ligand (biochemistry) , covalent bond , crystallography , phosphine oxide , phosphine , stereochemistry , inorganic chemistry , nuclear magnetic resonance , organic chemistry , receptor , biochemistry , physics , catalysis
Given the importance of Fe–NO complexes in both human biology and the global nitrogen cycle, there has been interest in understanding their diverse electronic structures. Herein a redox series of isolable iron nitrosyl complexes stabilized by a tris(phosphine)borane (TPB) ligand is described. These structurally characterized iron nitrosyl complexes reside in the following highly reduced Enemark–Feltham numbers: {FeNO} 8 , {FeNO} 9 , and {FeNO} 10 . These {FeNO} 8–10 compounds are each low‐spin, and feature linear yet strongly activated nitric oxide ligands. Use of Mössbauer, EPR, NMR, UV/Vis, and IR spectroscopy, in conjunction with DFT calculations, provides insight into the electronic structures of this uncommon redox series of iron nitrosyl complexes. In particular, the data collectively suggest that {TPBFeNO} 8–10 are all remarkably covalent. This covalency is likely responsible for the stability of this system across three highly reduced redox states that correlate with unusually high Enemark–Feltham numbers.