Untersuchung von neuartigen Oxidfluoriden der späten Übergangsmetalle mittels Matrixisolationsspektroskopie
Zusammenfassung der Projektergebnisse
High-valent late transition metal complexes bearing multiple bonded, terminal M-O groups persistently attract attention. They are reactive intermediates in various oxidation reactions, and in hydrogen and oxygen atom transfer processes. Additionally, due to their peculiar electronic structures they often show an electrophilic radical oxyl (O - ) - character than that of a closed-shell terminal oxo ligand (O2-). Many early transition metal complexes with multiple M-O bonds are common, however, oxo complexes of group 11 and 10 metals are rarely investigated due to experimental and computational challenges. In this project, the target molecules were synthesized by the matrix-isolation technique and characterized by infrared (IR) spectroscopy combined with quantum-chemical methods to analyze their electronic structures and harmonic frequencies. The linear oxo monofluoride OMF, the T-shape oxo difluorides OMF2 (M = Au, Ag, Ni, Pd, Pt) and the planar oxo trifluoride OPtF3 as well as the hypofluorite FOPdF have been observed and spectroscopically characterized. In combination with quantum-chemical calculations the nature of the chemical bond has been investigated in detail for these species.
Projektbezogene Publikationen (Auswahl)
- “Oxygen radical character in group 11 oxygen fluorides” Nature Communications 2018, 9:1267
Lin Li, Tony Stüker, Stefanie Kieninger, Dirk Andrae, Tobias Schlöder, Yu Gong, Lester Andrews, Helmut Beckers, Sebastian Riedel
(Siehe online unter https://doi.org/10.1038/s41467-018-03630-0) - „Molecular Oxofluorides OMFn of Nickel, Palladium and Platinum; Oxyl Radicals with Moderate Ligand Field Inversion” Inorganic Chemistry Frontiers 2021, 8, 1215 - 1228
Lin Li, Helmut Beckers, Tony Stüker, Tilen Lindič, Tobias Schlöder, Dirk Andrae, Sebastian Riedel
(Siehe online unter https://doi.org/10.1039/D0QI01151G)
