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Redox‐Active Ligand‐Induced Homolytic Bond Activation
Author(s) -
Broere Daniël L. J.,
Metz Lotte L.,
de Bruin Bas,
Reek Joost N. H.,
Siegler Maxime A.,
van der Vlugt Jarl Ivar
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201410048
Subject(s) - homolysis , chemistry , ligand (biochemistry) , intramolecular force , redox , bond cleavage , photochemistry , bridging ligand , stereochemistry , radical , molecule , catalysis , receptor , inorganic chemistry , organic chemistry , biochemistry
Coordination of the novel redox‐active phosphine‐appended aminophenol pincer ligand (PNO H2 ) to Pd II generates a paramagnetic complex with a persistent ligand‐centered radical. The complex undergoes fully reversible single‐electron oxidation and reduction. Homolytic bond activation of diphenyldisulfide by the single‐electron reduced species leads to a ligand‐based mixed‐valent dinuclear palladium complex with a single bridging thiolate ligand. Mechanistic investigations support an unprecedented intramolecular ligand‐to‐disulfide single‐electron transfer process to induce homolytic SS cleavage, thereby releasing a thiyl (sulfanyl) radical. This could be a new strategy for small‐molecule bond activation.