Redox-Active-Ligand-Mediated Formation of an Acyclic Trinuclear Ruthenium Complex with Bridging Nitrido Ligands.
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 NaN3 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 N2 . The trinuclear omplex is reactive toward TEMPO-H, tin hydrides, thiols, and dihydrogen.
Homogeneous, Bioinspired and Supramolecular Catalysis, Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098, XH, Amsterdam, The Netherlands.
Bidraha
B
Bagh
Homogeneous, Bioinspired and Supramolecular Catalysis, Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098, XH, Amsterdam, The Netherlands.
Daniël L J
DL
Broere
Small Molecule X-ray Crystallography Facility, Department of Chemistry, John Hopkins University, Baltimore, MD, 21218, USA.
Maxime A
MA
Siegler
Homogeneous, Bioinspired and Supramolecular Catalysis, Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098, XH, Amsterdam, The Netherlands. j.i.vandervlugt@uva.nl.
Jarl Ivar
JI
van der Vlugt
azides; density functional calculations; redox chemistry; ruthenium; structure determination