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Theoretical Chemistry Accounts

, Volume 110, Issue 3, pp 196–204 | Cite as

The migratory insertion of carbon monoxide and methyl isocyanide into zirconium–carbon and titanium–carbon bonds anchored to a calix[4]arene moiety: a dynamical density functional study

  • Filippo De Angelis
  • Simona Fantacci
  • Antonio Sgamellotti
  • Nazzareno Re
Article

Abstract

The energetics and reaction mechanism of the migratory insertion of carbon monoxide and methyl isocyanide into the zirconium–carbon and titanium–carbon bonds in [calix[4](OMe)2(O)2M–Me2], (M=Zr, Ti), have been investigated by combining static and dynamic density functional calculations. Two steps have been characterized: the coordination of the incoming nucleophilic moiety leading to relatively stable facial adducts; its subsequent insertion into the M–C bond, leading to η2-bound acyl or iminoacyl complexes, providing a rationale for the different behavior of CO and MeNC towards both insertion and deinsertion reactions. Our results indicate that the rate-determining step for the overall MeNC insertion into the M–C bond is its coordination to the electron-deficient metal center, with the titanium system featuring a higher energy barrier (12.7 versus 5.5 kcal mol−1). Ab initio molecular dynamics simulations have been performed on the Zr system by means of the Car–Parrinello method, to study the hitherto inaccessible mechanistic features of the insertion reactions.

Keywords

Migratory insertion – Calix[4]arene moiety – Dynamical density functional calculations 

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Copyright information

© Springer-Verlag Berlin Heidelberg 2003

Authors and Affiliations

  • Filippo De Angelis
    • 1
  • Simona Fantacci
    • 1
  • Antonio Sgamellotti
    • 1
  • Nazzareno Re
    • 2
  1. 1.Istituto CNR di Scienze e Tecnologie Molecolari (ISTM)c/o Dipartimento di Chimica, Università di PerugiaPerugiaItaly
  2. 2.Facoltà di FarmaciaUniversità G. D’AnnunzioChietiItaly

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