Reactions of the arylated TREN derivatives N(CH2CH2NHAr)(3) [Ar = 2,4,6-C6Me3H2 (H3TMT), 3,5-(C6Bu2H3)-H-t (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. (C) 2000 Elsevier Science S.A. All rights reserved
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