SAMOP 2023 – scientific programme

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MO: Fachverband Molekülphysik

MO 2: Photochemistry

MO 2.3: Talk

Monday, March 6, 2023, 11:30–11:45, F142

Ultrafast Photochemistry of Metallo-Nitrenes — •Markus Bauer¹, Till Schmidt-Räntsch², Luis Domenianni¹, Sven Schneider², and Peter Vöhringer¹ — ¹Clausius Institut für physikalische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Deutschland — ²Institut für Anorganische Chemie, Georg-August-Universität Göttingen, Deutschland

Metallo-nitrenes, formed by the photochemical decomposition of metallo-azides, have recently shown to be promising complexes for chemical catalysis, specifically for nucleophilic metallo-nitrene C-H insertion.^[1] The exact reaction pathways, as well as the electronic structures of intermediate species remain so far largely unknown.

In this work, the photochemistry of the square-planar [M(N₃)(PNP)] (PNP=N(CHCHP^tBu₂)₂, M=Pd, Pt) complexes after excitation with 320 nm light were investigated using ultrafast UV-pump mIR-probe and time resolved Fourier transform IR-spectroscopy.

The data reveal that dinitrogen cleavage from the photolabile azide group occurs from the triplet state on a time scale in excess of 1 ns. The quantum yield for nitrene formation depends on the nature of the metal.

[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;