KIT | KIT-Bibliothek | Impressum | Datenschutz

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

Wenzel, Jonas O. 1; Werner, Johannes 2; Allgaier, Alexander; Slageren, Joris van; Fernández, Israel; Unterreiner, Andreas-Neil ORCID iD icon 2; Breher, Frank 1
1 Institut für Anorganische Chemie (AOC), Karlsruher Institut für Technologie (KIT)
2 Institut für Physikalische Chemie (IPC), Karlsruher Institut für Technologie (KIT)

Abstract:

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.


Verlagsausgabe §
DOI: 10.5445/IR/1000175661
Veröffentlicht am 28.10.2024
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Anorganische Chemie (AOC)
Institut für Physikalische Chemie (IPC)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 06.05.2024
Sprache Englisch
Identifikator ISSN: 1433-7851, 1521-3773
KITopen-ID: 1000175661
Erschienen in Angewandte Chemie International Edition
Verlag John Wiley and Sons
Band 63
Heft 19
Seiten Art.-Nr.: 202402885
Vorab online veröffentlicht am 04.04.2024
Nachgewiesen in Web of Science
Scopus
Dimensions
KIT – Die Forschungsuniversität in der Helmholtz-Gemeinschaft
KITopen Landing Page