Freiburg 2024 – scientific programme

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MO: Fachverband Molekülphysik

MO 21: Ultrafast Dynamics II

MO 21.3: Talk

Thursday, March 14, 2024, 15:00–15:15, HS 3044

Ultrafast Formation of Metallo-Nitrenes — •Markus Bauer, Luis Domenianni, and Peter Vöhringer — Clausius Institut für physikalische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Deutschland

Nitrenes have shown great potential as nitrogen-transfer reagents, owing to their high reactivity. For the same reason they are often found only as transient species and have to be prepared in-situ.[1] Therefore, to utilize their synthetic potential to the fullest, a firm understanding of the primary processes leading up to their formation is crucial.

Herein, a set of square-planar diazide complexes[2], [M(N3)2(dppe)] (dppe=1,2-Bis(diphenylphosphino)ethan, M=Ni, Pd, Pt) was studied using ultrafast UV-pump-mIR-probe and time-resolved FTIR-spectroscopy. For all complexes nitrene formation is observed, with an increase of the quantum yield dependent on the mass of the metal. Additionally an intermediate triplet state preceding the nitrene formation could be identified.

Literature: [1] T. Schmidt-Räntsch, H. Verplancke, J. N. Lienert, S. Demeshko, M. Otte, G. P. Van Trieste, K. A. Reid, J. H. Reibenspies, D. C. Powers, M. C. Holthausen, S. Schneider, Angew. Chem. Int. Ed. 2022, 61, e202115626. [2] Hennig, H., Hofbauer, K., Handke, K., Stich, R., 1997. Angew. Chem. Int. Ed. Engl. 36, 408*410.

Keywords: Pump-Probe Spectroscopy; Femtosecond Spectroscopy; Vibrational Spectroscopy; Photochemistry; Nitrenes