Bonn 2025 – wissenschaftliches Programm
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MO: Fachverband Molekülphysik
MO 5: Ultrafast Dynamics I
MO 5.1: Vortrag
Dienstag, 11. März 2025, 11:00–11:15, HS XVI
Ultrafast Excited State Dynamics of the Nitrene Formation in Bis-Carbene-Ni/Pd/Pt-Azides — •Markus Bauer1, Frederik Scherz2, Luis Ignacio Domenianni1, Anna Pavun3, Biprajit Sarkar4, Stefan Hohloch3, Vera Krewald2, and Peter Vöhringer1 — 1Clausius Institut für physikalische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Deutschland — 2Fachbereich Chemie, Technische Universität Darmstadt, Deutschland — 3Department of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Österreich — 4Fachbereich Biologie, Chemie, Pharmazie, Freie Universität Berlin, Deutschland
Nitrenes are highly reactive subvalent nitrogen species that are often used as intermediates in many organic and pharmaceutical syntheses.
We investigated the UV-induced photochemistry of three square-planar metal-azides coordinated by a tridentate ligand possessing two carbene and one amido donor (Metal=Ni, Pd, Pt). Utilizing femtosecond UV-pump-mIR-probe and UV-pump-Vis-probe spectroscopy, we were able to record the primary photochemical processes following the UV-excitation, which differ significantly depending on the metal center. Furthermore, we succeeded in identifying the key intermediates preceding nitrene formation using quantum chemical calculations.
The nickel-based complex undergoes almost exclusively ground-state recovery (GSR) and seems to remain on the singlet surface, while both the palladium, as well as the platinum species exhibit complex, but distinct intersystem crossing dynamics. Additionally, the quantum yield increases significantly with the mass of the metal center.
Keywords: Pump-Probe Spectroscopy; Femtosecond Spectroscopy; Vibrational Spectroscopy; Nitrenes