Synthesis of Rh super(III) Anilido, Hydroxide, and Methoxide Complexes

The octahedral Rh super(III) complexes [( super()tpy) sub(2)Rh(XH) sub(2)][OTf] sub(3) ( super()tpy = 4,4'-di-tert-butyl-2,2'-bipyridyl; X = NHPh or OH; OTf = trifluoromethanesulfonate), [( super()tpy) sub(2)Rh(X) sub(2)][OTf] (X = NHPh or OH), [( super()tpy) sub(2)Rh(NHPh)(NH sub(2)Ph)][OTf] sub(2), [( super()tpy) sub(2)Rh(Me)(NH sub(2)Ph)][OTf][BAr' sub(4)] (BAr' sub(4) = tetrakis[(3,5-bis-trifluoromethyl)phenyl]borate), [( super()tpy) sub(2)Rh(Me)(NHPh)][BAr' sub(4)], [( super()tpy) sub(2)Rh(OMe)(Cl)]Cl, and [(bpy)Rh(X) sub(2)][PF sub(6)] (bpy = 2,2'-bipyridyl; X = OH, OMe) have been synthesized and characterized by super(1)H, super(13)C{ super(1)H}, and super(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 [( super()tpy) sub(2)Rh(Me)(NH sub(2)Ph)] super(2+), [( super()tpy) sub(2)Rh(NH sub(2)Ph) sub(2)] super(3+), [( super()tpy) sub(2)Rh(NHPh) sub(2)] super(+), and [( super()tpy) sub(2)Rh(NHPh)(NH sub(2)Ph)] super(2+) is included. Octahedral and d super(6) complexes with pi -donating ligands often exhibit interesting reactivity. Herein, new examples of Rh super(III) complexes with pi -donating anilido, hydroxide, and methoxide ligands are reported.