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Dynamical density functional study of the multistep CO insertion into zirconium-carbon bonds anchored to a calix[4]arene moiety

Organometallics, ISSN: 0276-7333, Vol: 20, Issue: 19, Page: 4031-4039
2001
  • 13
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  • 6
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Metrics Details

  • Citations
    13
    • Citation Indexes
      13
  • Captures
    6

Article Description

The multistep migratory insertion reaction of CO into the zirconium-carbon bonds in [calix[4](OMe)(O)ZrMe] has been investigated by means of both static and dynamic density functional calculations. A relatively stable facial CO complex has been observed with a negligible barrier for CO insertion into one of the Zr-Me bonds, leading to the formation of an η-acyl complex. The insertion of the residual alkyl group into the acyl moiety, leading to an η-bound acetone, has also been investigated, and a small energy barrier, 2.3 kcal/mol, has been found. Dynamics simulations have been performed on the [calix[4](OMe)(O)Zr-(Me)]-CO adduct in order to study the detailed features of the whole multistep insertion and show that the migratory insertion leads to the formation of an out-of-plane η-acyl complex, which is readily converted into the more stable η-acyl isomer within 1.5 ps. The subsequent methyl to acyl migration has been observed within 5 ps, leading to the formation of the η-bound acetone by a facial attack of the migrating methyl to the acyl carbon. A comparison with the migratory insertion of CO into the metal-alkyl bond in (Me)Zr(Cp) has been performed, showing substantial differences in the reactivity of the calix[4]arene and bis(cyclopentadienyl) substrates.

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