Synthesis and structural characterization of tris (phenolate)amine complexes of antimony derived from [κ4-N(CH2ArBu2tO)3]Sb

The antimony aryloxide compound [κ4-N(CH2ArBu2tO)3]Sb may be readily obtained via the reaction of Sb(OEt)3 with tris(3,5-di-t  -butyl-2-hydroxybenzyl)amine, N(CH2ArBu2tOH)3.[κ4-N(CH2ArBu2tO)3]Sb forms the adduct [κ4-N(CH2ArBu2tO)3]Sb(OSMe2) upon treatment with Me2SO, and comparison of the molecular structure of [κ4-N(CH2ArBu2tO)3]Sb(OSMe2) with that of [κ4-N(o-C6H4O)3]Sb(OSMe2) demonstrates that the Sb–OSMe2 bond length in the former complex is significantly longer than that in the latter. This observation indicates that the [κ4-N(CH2ArBu2tO)3] ligand engenders a less Lewis acidic antimony center than does [κ4-N(o–C6H4O)3][κ4-N(o–C6H4O)3]. [κ4-N(CH2ArBu2tO)3]Sb exhibits diverse reactivity. For example, treatment of [κ4-N(CH2ArBu2tO)3]Sb with AcOH cleaves one of the Sb–O bonds to give [κ3-N(CH2ArBu2tO)2(CH2ArBu2tOH)]Sb(κ1-O2CMe), Br2 undergoes oxidative addition to give N(CH2ArBu2tO)3]SbBr2, while Me3NO · 2H2O yields the oxo and hydroxo complexes {[κ4-N(CH2ArBu2tO)3]Sb(μ-O)}2, [κ4-N(CH2ArBu2tO)3]Sb(OH)2, and {[κ4-N(CH2ArBu2tO)3]SbVO}4{Sb4IIIO6}.

Graphical abstractThe antimony aryloxide compound [κ4-N(CH2ArBu2tO)3]Sb reacts with Br2 to give N(CH2ArBu2tO)3]SbBr2, while Me3NO · 2H2O yields the oxo and hydroxo complexes {[κ4-(N(CH2ArBu2tO)3]Sb(μ-O)}2, [κ4-N(CH2ArBu2tO)3]Sb(OH)2, and {[κ4-N(CH2ArBu2tO)3]SbVO}4{Sb4IIIO6}.Figure optionsDownload full-size imageDownload as PowerPoint slide