First observation of a [1,7] boron shift - Three independent fluxional processes in the tricarbonyliron complex of cycloheptatrienyl(dipropyl)borane

Ilya D. Gridnev, Oleg L. Tok, Mikhail E. Gurskii, Yuri N. Bubnov

Research output: Contribution to journalArticlepeer-review

15 Citations (Scopus)

Abstract

The fluxional behavior of [1-4-η4 - exo - 7 - dipropylborylcyclohepta -1,3,5-triene]tricarbonyliron (14) has been studied by dynamic NMR. The 2D 1H and 13C EXSY NMR experiments carried out at various temperatures revealed that three independent fluxional processes occur in 14. The fastest rearrangement is a [1,7] B sigmatropic shift accompanied by [1,2] Fe migration (EA = 71.2 ± 2.3 kJ mol -1, ln A = 32±1). Two other rearrangements also take place: [1,3] B sigmatropic and [1,3] Fe haptotropic migrations. The analysis of the observed selectivity towards [1,j] B sigmatropic shifts ([1,3] and [1,7] B shifts are observed, but [1,5] B shifts are not) in terms of theoretical predictions gives reason to assume that the [1,j] boron migrations occur with inversion of configuration at the migrating atom.

Original languageEnglish
Pages (from-to)1483-1488
Number of pages6
JournalChemistry - A European Journal
Volume2
Issue number11
DOIs
Publication statusPublished - 1996 Dec 1
Externally publishedYes

Keywords

  • Boron compounds
  • Fluxionality
  • Iron complexes
  • NMR spectroscopy
  • Rearrangements

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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