Lipophilic halogenozirconocene(III) complexes: [{Zr[η-C5H3(SiMe3)2-1,3]2(µ-Cl)}2], [NBun4][Zr{η-C5H3(SiMe3)2-1,3}2Cl2] and [Zr{η-C5H3(SiMe3)2-1,3}2Cl2]

Abstract
Treatment of [Zr{η-C5H3(SiMe3)2-1,3}2X2] with Na–Hg in tetrahydrofuran (THF) affords the blue (X = Cl 2a or Br) or green (X = I) crystalline complexes [{Zr[η-C5H3(SiMe3)2-1,3]2(µ-X)}2], with characteristic ZrIII ESR spectra (PhMe, 300 K) and exceptionally long (3.86–4.17 Å) Zr ⋯ Zr contacts; 2a is susceptible to facile Zr(µ-Cl)2Zr bridge-cleavage upon reaction with either a neutral (e.g. THF) or an anionic (e.g. Cl) nucleophile, as in its conversion into [NBun 4][Zr{η-C5H3(SiMe3)2-1,3}2Cl2].

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