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.

将四正丁基铵四氯氮合钌(VI)（[n-Bu4N][Ru(N)Cl4]）与[AgLOEt]（其中LOEt- = [(η5-C5H5)Co{P(O)(OEt)2}3]-，即(η5-环戊二烯基)三(二乙氧基膦氧基)合钴(-1)配体阴离子）反应，得到钌(VI)氮合配合物[LOEtRu(N)Cl2]（化合物1）。该配合物与三苯基膦（PPh3）反应，生成钌(IV)膦亚胺基配合物[LOEtRu(NPPh3)Cl2]（化合物2）。化合物2的循环伏安曲线显示，相对于二茂铁/二茂铁正离子参比体系，Ru(IV)/Ru(III)电对的氧化还原电位约为0 V。将化合物1与三甲基胺-N-氧化物（Me3NO）反应，得到[LOEtRu(NO)Cl2]（化合物3）；该配合物与三氟甲磺酸银（Ag(OTf)，其中OTf-为三氟甲磺酸根（triflate）配体）反应，得到氯桥联四核钌/银配合物[LOEtRu(NO)Cl2]2[Ag(OTf)]2（化合物4）。将化合物1与硫代硫酸钠（Na2S2O3）反应，得到硫代亚硝基配合物[LOEtRu(NS)Cl2]（化合物5）。化合物1至4的固态结构已通过X射线晶体学得以解析确证。