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

ABSTRACT: Recent DFT calculations have suggested that iron nitrosyl triarylcorrole complexes have substantial {FeNO}⁷-corrole^•2- 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}⁷ 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_NO and changes in the corrole vibrational frequencies. DFT calculations, which showed that the electron was mostly add

SUBMITTER: Rahman MH 

PROVIDER: S-EPMC7997370 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature