Get access

An Integrated NMR and DFT Study on the Single Insertion of α-Olefins into the M[BOND]C Bond of Group 4 Metallaaziridinium Ion Pairs

Authors

  • Dr. Luca Rocchigiani,

    Corresponding author
    1. Dipartimento di Chimica, Università degli Studi di Perugia, Via Elce di sotto 8, I-06123, Perugia (Italy), Fax: (+39) 075-5855598
    • Dipartimento di Chimica, Università degli Studi di Perugia, Via Elce di sotto 8, I-06123, Perugia (Italy), Fax: (+39) 075-5855598
    Search for more papers by this author
  • Dr. Gianluca Ciancaleoni,

    1. Istituto del CNR di Scienze e Tecnologie Molecolari (CNR-ISTM) c/o Dipartimento di Chimica, Università degli Studi di Perugia, I-06123, Perugia (Italy)
    Search for more papers by this author
  • Dr. Cristiano Zuccaccia,

    1. Dipartimento di Chimica, Università degli Studi di Perugia, Via Elce di sotto 8, I-06123, Perugia (Italy), Fax: (+39) 075-5855598
    Search for more papers by this author
  • Prof. Dr. Alceo Macchioni

    Corresponding author
    1. Dipartimento di Chimica, Università degli Studi di Perugia, Via Elce di sotto 8, I-06123, Perugia (Italy), Fax: (+39) 075-5855598
    • Dipartimento di Chimica, Università degli Studi di Perugia, Via Elce di sotto 8, I-06123, Perugia (Italy), Fax: (+39) 075-5855598
    Search for more papers by this author

Abstract

The reactions of metallaaziridinium ion pairs [Cp2M(η2-CH2NMePh)][B(C6F5)4] [M=Zr (1), Hf (2)] with 1-hexene and 2-methyl-1-heptene were investigated by means of NMR spectroscopy and DFT calculations. We found that a single insertion of the olefin into the M[BOND]C bond led to the formation of stable five-membered heterocycles (36). The reactions were 1,2-regioselective and afforded two diastereoisomers whose ratio was mainly controlled by the nature of the olefin, whilst the nature of the metal only played a marginal role. In particular, the reaction with 1-hexene was found to be not only more favored than that with 2-methyl-1-heptene from a thermodynamic point of view but it was also more diastereoselective. In all cases, the observed diastereoisomeric ratio was dictated by thermodynamics because the products interconverted into each other, as indicated by EXSY NMR spectroscopy and by DFT calculations.

Get access to the full text of this article

Ancillary