Reactive metal–ligand (M–L) multiply bonded species, such as metal nitrides, oxos, and nitrenes, are critical reactive intermediates in both synthetic and biological C–H functionalization chemistry. The exquisite reactivity of intermediates capable of functionalizing C–H bonds, renders these complexes transient and challenging to observe during catalysis or to characterize structurally. Low-temperature syntheses of these reactive species, for example via cryogenic photochemistry, can provide access to reactive structures under conditions that support direct characterization of these species, however, in many cases, the required synthetic chemistry is not available. This talk will present our efforts to develop new photochemical strategies for low-temperature synthesis of reactive M–L multiply bonded complexes. We will specifically discuss photogenerated Ru2 nitrides and Rh2 nitrenes, both of which are important intermediates in C–H amination chemistry. The development of low-temperature synthetic methods has allowed the direct structural characterization of the critical nitrene intermediate by a variety of steady-state and time-resolved techniques, including cryogenic photocrystallography.

Photosynthesis and direct characterization of reactive metal–ligand multiply bonded intermediates

256th National Meeting (2018)

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