Two new catalytic systems for hydrogen-atom transfer (HAT) catalysis involving the N-H bonds of titanocene(III) complexes with pendant amide ligands are reported. In a monometallic system, a bifunctional catalyst for radical generation and reduction through HAT catalysis depending on the coordination of the amide ligand is employed. The pendant amide ligand is used to activate Crabtree's catalyst to yield an efficient bimetallic system for radical generation and HAT catalysis.
Catalytic systems involving titanocene complexes with pendant amide ligands are described to catalyze the hydrogen‐atom transfer reaction to yield the corresponding alcohols.
Zwei neue katalytische Systeme für die HAT‐Katalyse mit N‐H‐Bindungen Amid‐substituierter Titanocen(III)‐Komplexe werden vorgestellt. In einem Monometallsystem wird ein bifunktioneller Katalysator für die Radikalgenerierung und ‐reduktion durch HAT‐Katalyse eingesetzt. Diese Bifunktionalität hängt von der Koordination des Amidliganden ab. In einem Dimetallsystem aktivieren Amid‐substituierte Titanocen(III)‐Komplexe Crabtrees Katalysator für die Radikalgenerierung und HAT‐Katalyse.
Coupling catalytic cycles through metal–ligand bifunctional catalysis or cooperative catalysis is like dancing the tango. In their Communication on page 1523 ff., A. Gansäuer and co‐workers show that amides can be activated for radical reduction by amide‐substituted titanocene(III) catalysts or through cooperative catalysis with titanocenes and Crabtree's catalyst (graphic design by Dina Schwarz G. Henriques).
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