Published September 19, 2016 | Supplemental Material + Accepted Version
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A Triad of Highly Reduced, Linear Iron Nitrosyl Complexes: {FeNO}⁸⁻¹⁰

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Abstract

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.

Additional Information

© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Received: June 2, 2016; Revised: July 10, 2016; First published: 25 August 2016. This research was supported by the NIH (GM-070757) and an NSF Graduate Research Fellowship to M.J.C. We thank Larry Henling and Dr. Michael K. Takase for crystallographic assistance. We acknowledge Dr. Gaël Ung for preliminary data on the {TPBFeNO}^8 complex and helpful discussions.

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Accepted Version - nihms824008.pdf

Supplemental Material - anie201605403-sup-0001-misc_information.pdf

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