Synthesis and Structural Characterization of New Zirconium(IV) Bent Metallocenes comprising η8‐Cyclooctatetraenyl and Bulky Cyclopentadienyl Ligands

The new zirconium bent metallocenes (COT)Zr(CptBu2)Cl (1) and (COT)Zr(Cp′′)Cl (2) were synthesized in a straightforward manner and in high yields (1: 91 %, 2: 86 %) by treatment of in situ‐prepared (COT)ZrCl2(THF) with 1 equiv. of K(CptBu2) or K(Cp′′), respectively (COT = η8‐cyclooctatetraenyl; CptBu2 = η5‐1,3‐di‐tert‐butylcyclopentadienyl; Cp′′ = η5‐1,3‐bis(trimethylsilyl)cyclopentadienyl). Subsequent reaction of 1 with 1 equiv. of phenyllithium afforded the σ‐phenyl derivative (CptBu2)Zr(COT)Ph (3) as orange crystals in 83 % isolated yield. All three new compounds were structurally characterized through single‐crystal X‐ray diffraction.