Preparation and characterization of monomeric and dimeric group IV metallocene dihydrides having alkyl- substituted cyclopentadienyl ligands

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Abstract

A series of zirconocene dihydride complexes of the general form [(RnCp)2ZrH2]x having substituted cyclopentadienyl ligands has been prepared by hydrogenation of the corresponding dimethyl complexes. The most sterically crowded members (Cp*(η5-C5HMe4)ZrH2, (Cp* = (η5-C5Me5)), Cp*{η5-C5H3-1,3-(CMe 3)2}ZrH2 and {η5-C5H3-1,3-(CMe3) 2}2ZrH2) are monomeric; those less crowded members ([Cp*{η5-C5H4(CMe 3)}ZrH2]2, [Cp*(THI)ZrH2]2 (THI = η5-tetrahydroindenyl), and [{η5-C5H3-1,3-(CHMe2) 2}2ZrH2]2) are predominantly dimeric in benzene solution. Cp*{η5-C5H3-1,3-(CHMe 2)2}ZrH2 and (η5-C5HMe4)2ZrH2 exist as equilibrium mixtures of monomer and dimer in benzene solution. The hydride ligands rapidly exchange with D2, affording the dideuteride complexes. Deuterium incorporation into some of the substituents on the cyclopentadienyl rings of the monomeric dihydride complexes is also observed. The X-ray structures of Cp*2HfH2, Cp*{η5-C5H4(CMe 3)}ZrCl2, Cp*{η5-C5H3-1,3-(CHMe 2)2}ZrCl2 and {η5-C5H3-1,3-(CMe3) 2}2ZrCl2 are reported.

Original languageEnglish (US)
Pages (from-to)1873-1881
Number of pages9
JournalOrganometallics
Volume18
Issue number10
DOIs
StatePublished - May 10 1999
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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