Mononuclear Amido and Binuclear Imido Zirconium Complexes Supported by Dibenzotetraaza[14]annulene Ligands. X-ray Structure of [(Me<sub>4</sub>taa)Zr(μ-NR)<sub>2</sub>Zr(NHR)<sub>2</sub>] (R = Bu<sup>t</sup> or 2,6-C<sub>6</sub>H<sub>3</sub>Me<sub>2</sub>)
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Reaction of 2 equiv of Li[NH-2,6-C6H3R2] with [(Me4taa)ZrCl2] (Me4taaH2 = tetramethyldibenzotetraaza[14]annulene) gives the bis(amido) derivatives [(Me4taa)Zr(NH-2,6-C6H3R2)2] [R = Pri (1) and Me (2)]. Addition of Me4taaH2 to [Zr(N-2,6-C6H3Pri2)(NH-2,6-C6H3Pri2)2(py)2] also affords 1. The reaction of 2 equiv of aryl or alkyl amines H2NR with the bis(alkyl) complex [(Me4taa)Zr(CH2SiMe3)2] is the most versatile method for preparing [(Me4taa)Zr(NHR)2] (R = 2,6-C6H3Pri2, 2,6-C6H3Me2, Ph, or But). Reaction of 1 equiv of Me4taaH2 with the binuclear complexes [(ButNH)2Zr(μ-NBut)2Zr(NHBut)2] or [(py)(HN-2,6-C6H3Me2)2Zr(μ-N-2,6-C6H3Me2)2Zr(NH-2,6-C6H3Me2)2(py)] gives the asymmetrically substituted derivatives [(Me4taa)Zr(μ-NR)2Zr(NHR)2] [R = But (6) or 2,6-C6H3Me2 (8)], which have been crystallographically characterized.
