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Infrared Spectroelectrochemistry of Iron-Nitrosyl Triarylcorroles. Implications for Ligand Noninnocence.

07:00 EST 13th February 2020 | BioPortfolio

Summary of "Infrared Spectroelectrochemistry of Iron-Nitrosyl Triarylcorroles. Implications for Ligand Noninnocence."

Recent DFT calculations have suggested that iron nitrosyl triarylcorrole complexes have substantial {FeNO}-corrole character. With this formulation, reduction of Fe(C)(NO) complexes, where C = triarylcorrole, should be centered on the corrole macrocycle rather than on the {FeNO} moiety. To verify this proposition, visible and infrared spectroelectrochemical studies of Fe(C)(NO) were carried out and the results were interpreted using DFT (B3LYP/STO-TZP) calculations. The first reduction of Fe(C)(NO) led to significant changes in the Soret and Q-band regions of the visible spectrum as well as to a significant downshift in the ν and changes in the corrole vibrational frequencies. DFT calculations, which showed that the electron was mostly added to the corrole ligand (85%), were also able to predict the observed shifts in the ν and corrole bands upon reduction. These results underscore the importance of monitoring both the corrole and nitrosyl vibrations in ascertaining the site of reduction. By contrast, the visible spectroelectrochemistry of the second reduction revealed only minor changes in the Soret band upon reduction, consistent with the reduction of the FeNO moiety.

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This article was published in the following journal.

Name: Inorganic chemistry
ISSN: 1520-510X
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