Synthesis and Structures of Zirconium and Hafnium Alkyl Complexes That Contain [H<sub>3</sub>CC(2-C<sub>5</sub>H<sub>4</sub>N)(CH<sub>2</sub>NAr)<sub>2</sub>]<sup>2-</sup> ([ArNpy]<sup>2-</sup>; Ar = Mesityl, Triisopropylphenyl) Ligands
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We report the synthesis of the arylated diamidopyridine ligands [H3CC(2-C5H4N)(CH2NAr)2]2- ([ArNpy]2-; Ar = 2,4,6-Me3C6H2 (Mes), 2,4,6-(i-Pr)3C6H2 (Trip)). [ArNpy]M(NMe2)2 (M = Zr, Hf) complexes were prepared by treating M(NMe2)4 with H2[ArNpy], while [ArNpy]MCl2 was prepared in a reaction between [ArNpy]M(NMe2)2 and Me3SiCl. Zirconium dialkyl complexes that were prepared include [MesNpy]ZrR2 (R = methyl, benzyl, neopentyl, isobutyl), [MesNpy]Zr(THF)Me2, [Li(Et2O)]{[MesNpy]ZrMe3}, and [TripNpy]Zr(i-Bu)2. Hafnium [MesNpy]HfR2 complexes are relatively stable, even when β-protons are present in R (R = Me, Et, n-Pr, n-Bu, i-Bu, i-Pr). Monoalkyl monochloro hafnium complexes that were prepared include [MesNpy]Hf(i-Pr)Cl and [MesNpy]Hf(t-Bu)Cl. X-ray studies were carried out for [MesNpy]ZrMe2, [MesNpy]Zr(THF)Me2, [Li(Et2O)]{[MesNpy]ZrMe3}, [TripNpy]Zr(i-Bu)2, [MesNpy]Hf(i-Pr)Cl, and [MesNpy]Hf(i-Pr)2.
