Unraveling Metal-Ligand Bonding in an HNO-Evolving {FeNO}⁶ Complex with a Combined X-ray Spectroscopic Approach.

ABSTRACT: Photolytic delivery of nitric oxide and nitroxide has substantial biomedical and phototherapeutic applications. Here, we utilized hard X-ray spectroscopic methods to identify key geometric and electronic structural features of two photolabile {FeNO}⁶ complexes where the compounds differ in the presence of a pendant thiol in [Fe(NO)(^TMSPS2)(^TMSPS2H)] and thioether in [Fe(NO)(^TMSPS2)(^TMSPS2CH₃)] with the former complex being the only transition metal system to photolytically generate HNO. Fe Kβ XES identifies the photoreactant systems as essentially Fe(II)-NO⁺, while valence-to-core XES extracts a NO oxidation state of +0.5. Finally, the pre-edge of the Fe high-energy-resolution fluorescence detected (HERFD) XAS spe

SUBMITTER: Gee LB 

PROVIDER: S-EPMC10876219 | biostudies-literature | 2023 Sep

REPOSITORIES: biostudies-literature