Electrophilic Ruthenium(VI) Nitrido Complex Containing Kläui's Oxygen Tripodal Ligand

Treatment of [n-Bu4N][Ru(N)Cl4] with [AgLOEt] (LOEt- = [(η5-C5H5)Co{P(O)(OEt)2}3]-) afforded the ruthenium(VI) nitrido complex [LOEtRu(N)Cl2] (1), which reacted with PPh3 to give the ruthenium(IV) phosphiniminato complex [LOEtRu(NPPh3)Cl2] (2). The cyclic voltammogram of 2 displays the RuIV/III couple at ca. 0 V vs ferrocenium/ferrocene. Treatment of 1 with Me3NO afforded [LOEtRu(NO)Cl2] (3), which reacted with Ag(OTf) (OTf- = triflate) to give the chloro-bridged tetranuclear ruthenium/silver complex [LOEtRu(NO)Cl2]2[Ag(OTf)]2 (4). Treatment of 1 with Na2S2O3 gave the thionitrosyl complex [LOEtRu(NS)Cl2] (5). The solid-state structures of 1−4 have been established by X-ray crystallography.