Complexes of zirconium with aryl substituted triamidoamines: molecular structures of amide and alkyl derivatives

Reactions of the arylated TREN derivatives N(CH2CH2NHAr)3 [Ar=2,4,6-C6Me3H2 (H3TMT), 3,5-C6But2H3 (H3TDT)] individually with Zr(NMe2)4 and Zr(CH2Ph)4 give the azazirconatranes [Zr(TMT)(NMe2)], [Zr(TDT)(NMe2)] and [Zr(TDT)(CH2Ph)] and unexpectedly [Zr(HTMT)(CH2Ph)2]. The molecular structures of [Zr(TMT)(NMe2)] and [Zr(TDT)(CH2Ph)] show that the triamidoamine ligand is arranged with the usual three-fold symmetry about the metal and that the aryl substituents form a bowl cavity with the apical ligand at the base. The reactions of the alkyl with dihydrogen lead to decomposition, and a hydride species such as that proposed in earlier studies could not be detected.