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Preparation of the Octahedral d6 Amido Complex TpRu(CO)(PPh3)(NHPh) (Tp = Hydridotris(pyrazolyl)borate):  Solid-State Structural Characterization and Reactivity

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posted on 07.11.2001, 00:00 by K. N. Jayaprakash, T. Brent Gunnoe, Paul D. Boyle
The reaction of TpRu(CO)(PPh3)(OTf) (2) with LiNHPh affords the amido complex TpRu(CO)(PPh3)(NHPh) (3) in 88% isolated yield. The amido complex 3 has been characterized by 1H NMR, 13C NMR, 31P NMR, elemental analysis, cyclic voltammetry, and a solid-state X-ray diffraction study. Variable temperature NMR studies have revealed a rotational barrier around the ruthenium−amido nitrogen bond of 3 of 12 kcal/mol (transformation of the major isomer to the minor isomer). The solid-state structure of 3 discloses a pyramidal amido moiety. Heating benzene solutions of the amido complex 3 and 1,4-cyclohexadiene or 9,10-dihydroanthracene results in no observable reaction. Reaction of complex 2 with excess aniline yields [TpRu(CO)(PPh3)(NH2Ph)][OTf] (4).