Synthesis of Rh III Anilido, Hydroxide, and Methoxide Complexes

The octahedral Rh III complexes [( t bpy) 2 Rh(XH) 2 ][OTf] 3 ( t bpy = 4,4′‐di‐ tert ‐butyl‐2,2′‐bipyridyl; X = NHPh or OH; OTf = trifluoromethanesulfonate), [( t bpy) 2 Rh(X) 2 ][OTf] (X = NHPh or OH), [( t bpy) 2 Rh(NHPh)(NH 2 Ph)][OTf] 2 , [( t bpy) 2 Rh(Me)(NH 2 Ph)][OTf][BAr′ 4 ] (BAr′ 4 = tetrakis[(3,5‐bis‐trifluoromethyl)phenyl]borate), [( t bpy) 2 Rh(Me)(NHPh)][BAr′ 4 ], [( t bpy) 2 Rh(OMe)(Cl)]Cl, and [(bpy)Rh(X) 2 ][PF 6 ] (bpy = 2,2′‐bipyridyl; X = OH, OMe) have been synthesized and characterized by 1 H, 13 C{ 1 H}, and 19 F 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 [( t bpy) 2 Rh(Me)(NH 2 Ph)] 2+ , [( t bpy) 2 Rh(NH 2 Ph) 2 ] 3+ , [( t bpy) 2 Rh(NHPh) 2 ] + , and [( t bpy) 2 Rh(NHPh)(NH 2 Ph)] 2+ is included.