Document Type

Article

Language

eng

Publication Date

2016

Publisher

American Chemical Society

Source Publication

Inorganic Chemistry

Source ISSN

0020-1669

Original Item ID

DOI: 10.1021/acs.inorgchem.5b02384

Abstract

The preparation and characterization of the iron octaethylporphyrin nitroxyl ion, [Fe(OEP)(NO)−], is reported. The complex was synthesized by the one-electron reduction of Fe(OEP)(NO) using anthracenide as the reducing agent. The compound was isolated as the potassium (2.2.2)cryptand salt. The anion was characterized using X-ray analysis with visible and infrared spectroscopy. The spectral features of the iron nitroxyl complex were consistent with previous literature reports. The important structural changes upon reduction were a significant decrease in the Fe–N–O bond angle from 142° to 127° and an increase in the N–O bond length from that in the starting nitrosyl moiety. The porphyrin ring became significantly less planar upon reduction, but the displacement of the iron atom from the 24-atom plane was essentially unchanged. In spite of the attempt to encapsulate the potassium ion with the (2.2.2)cryptand, significant interaction between K+ and the oxygen of the nitroxyl were observed, indicating a contact ion pair in the crystal structure. Comparison between the experimental structure and the DFT-calculated parameters were reported. The results are consistent with the Fe–N–O moiety being the site of the reduction, with little evidence for the reduction of the iron itself or the porphyrin ring. The proton NMR spectrum was also obtained, and the chemical shifts were significantly different from other S = 0 metalloporphyrin complexes. These shifts, though, were consistent with the DFT calculations.

Comments

Accepted version. Inorganic Chemistry, Vol. 55, No. 5 (2016): 2070-2075. DOI. © 2016 American Chemical Society. Used with permission.

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