Monocyclopentadienyl and mono(2-methoxyethylcyclopentadienyl) zirconium methyl complexes

The reactions of (η5-Cp)ZrCl3(DME) and (η5:η1-Cp°)ZrCl3 (Cp°=C5H4CH2CH2OMe) with 1–2 equivalents of MeLi or MeMgI and THF yield the mono- and dimethyl zirconium complexes (η5-Cp)ZrCl3−xMex(THF) and (η5:η1-Cp°)ZrCl3−xMex (x=1, 2), respectively. Reaction with three equivalents of MeMgI affords (η5-Cp)ZrMe3(THF) and (η5:η1-Cp°)ZrMe3. The reaction with three equivalents of MeLi affords (η5-Cp)2ZrMe2 or (η5-Cp°)2ZrMe2 and ZrMe4, as a result of disproportionation. The reaction of (η5:η1-Cp°)ZrMe3 with B(C6F5)3 in THF affords the cationic zirconium complex [(η5:η1-Cp°)ZrMe2(THF)][MeB(C6F5)3]. The chloride-bridged complex [(η5:η1-Cp°)Zr(μ-Cl)Me2]2 was characterized by single-crystal X-ray crystallography.