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

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...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2024-05, Vol.63 (19), p.e202402885-n/a
Main Authors: Wenzel, Jonas O., Werner, Johannes, Allgaier, Alexander, Slageren, Joris, Fernández, Israel, Unterreiner, Andreas‐Neil, Breher, Frank
Format: Article
Language:English
Subjects:
Alkylation
Aluminum
Atmospheric chemistry
Carbonyl compounds
Carbonyls
Charge transfer
Magnetic resonance spectroscopy
Main Group Chemistry
NMR spectroscopy
Non-Innocent Ligands
Organoaluminum Chemistry
Organometallic compounds
Photochemicals
Photochemistry
Quantum chemistry
Reactivity
Ultraviolet spectroscopy
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Summary: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. This work reports on the synthesis of varied bis(pyridylimino) isoindolide aluminum complexes and a detailed study of its charge‐transfer induced metal‐carbon bond homolysis in a transition‐metal mimicking fashion as well as following reactivity studies.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202402885