Synthesis of RhIII Anilido, Hydroxide, and Methoxide Complexes

The octahedral RhIII complexes [(tbpy)2Rh(XH)2][OTf]3 (tbpy = 4,4′‐di‐tert‐butyl‐2,2′‐bipyridyl; X = NHPh or OH; OTf = trifluoromethanesulfonate), [(tbpy)2Rh(X)2][OTf] (X = NHPh or OH), [(tbpy)2Rh(NHPh)(NH2Ph)][OTf]2, [(tbpy)2Rh(Me)(NH2Ph)][OTf][BAr′4] (BAr′4 = tetrakis[(3,5‐bis‐trifluoromethyl)phenyl]borate), [(tbpy)2Rh(Me)(NHPh)][BAr′4], [(tbpy)2Rh(OMe)(Cl)]Cl, and [(bpy)Rh(X)2][PF6] (bpy = 2,2′‐bipyridyl; X = OH, OMe) have been synthesized and characterized by 1H, 13C{1H}, and 19F NMR spectroscopy, elemental analysis, or high‐resolution mass spectrometry as well as single‐crystal X‐ray diffraction for some complexes. A comparison of the solid‐state structural data for [(tbpy)2Rh(Me)(NH2Ph)]2+, [(tbpy)2Rh(NH2Ph)2]3+, [(tbpy)2Rh(NHPh)2]+, and [(tbpy)2Rh(NHPh)(NH2Ph)]2+ is included. Octahedral and d6 complexes with π‐donating ligands often exhibit interesting reactivity. Herein, new examples of RhIII complexes with π‐donating anilido, hydroxide, and methoxide ligands are reported.