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Redox‐Active‐Ligand‐Mediated Formation of an Acyclic Trinuclear Ruthenium Complex with Bridging Nitrido Ligands
Author(s) -
Bagh Bidraha,
Broere Daniël L. J.,
Siegler Maxime A.,
van der Vlugt Jarl Ivar
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201603659
Subject(s) - chemistry , ruthenium , redox , bridging ligand , ligand (biochemistry) , pyridine , radical , medicinal chemistry , photochemistry , stereochemistry , inorganic chemistry , crystallography , crystal structure , catalysis , organic chemistry , receptor , biochemistry
Coordination of a redox‐active pyridine aminophenol ligand to Ru II followed by aerobic oxidation generates two diamagnetic Ru III species [ 1 a (cis) and 1 b (trans)] with ligand‐centered radicals. The reaction of 1 a / 1 b with excess NaN 3 under inert atmosphere resulted in the formation of a rare bis(nitrido)‐bridged trinuclear ruthenium complex with two nonlinear asymmetrical Ru‐N‐Ru fragments. The spontaneous reduction of the ligand centered radical in the parent 1 a / 1 b supports the oxidation of a nitride (N 3− ) to half an equivalent of N 2 . The trinuclear omplex is reactive toward TEMPO‐H, tin hydrides, thiols, and dihydrogen.