Visible-Light Activation of Diorganyl Bis(pyridylimino) Isoindolide Aluminum(III) Complexes and Their Organometallic Radical Reactivity.

Autor: Wenzel JO; Karlsruhe Institute of Technology (KIT), Institute of Inorganic Chemistry (AOC), Engesserstraße 15, 76131, Karlsruhe, Germany., Werner J; Karlsruhe Institute of Technology (KIT), Institute of Physical Chemistry (IPC), Fritz-Haber-Weg 2, 76131, Karlsruhe, Germany., Allgaier A; University of Stuttgart, Institute of Physical Chemistry, Pfaffenwaldring 55, 70569, Stuttgart, Germany., van Slageren J; University of Stuttgart, Institute of Physical Chemistry, Pfaffenwaldring 55, 70569, Stuttgart, Germany., Fernández I; Universidad Complutense de Madrid, Facultad de Ciencias Químicas, 28040, Madrid, Spain., Unterreiner AN; Karlsruhe Institute of Technology (KIT), Institute of Physical Chemistry (IPC), Fritz-Haber-Weg 2, 76131, Karlsruhe, Germany., Breher F; Karlsruhe Institute of Technology (KIT), Institute of Inorganic Chemistry (AOC), Engesserstraße 15, 76131, Karlsruhe, Germany.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 May 06; Vol. 63 (19), pp. e202402885. Date of Electronic Publication: 2024 Apr 04.
DOI: 10.1002/anie.202402885
Abstrakt: We report on the synthesis and characterization of a series of (mostly) air-stable diorganyl bis(pyridylimino) isoindolide (BPI) aluminum complexes and their chemistry upon visible-light excitation. The redox non-innocent BPI pincer ligand allows for efficient charge transfer homolytic processes of the title compounds. This makes them a universal platform for the generation of carbon-centered radicals. The photo-induced homolytic cleavage of the Al-C bonds was investigated by means of stationary and transient UV/Vis spectroscopy, spin trapping experiments, as well as EPR and NMR spectroscopy. The experimental findings were supported by quantum chemical calculations. Reactivity studies enabled the utilization of the aluminum complexes as reactants in tin-free Giese-type reactions and carbonyl alkylations under ambient conditions, which both indicated radical-polar crossover behavior. A deeper understanding of the physical fundamentals and photochemical process was provided, furnishing in turn a new strategy to control the reactivity of bench-stable aluminum organometallics.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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