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

I. D. Gridnev, O. L. Tok, M. E. Gurskii, Y. N. Bubnov

Research output: Contribution to journalArticle

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 (E(A) = 71.2 ± 2.3 kJ mol-1, In 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
JournalAngewandte Chemie - International Edition in English
Volume35
Issue number21
Publication statusPublished - 1996 Dec 1
Externally publishedYes

Keywords

  • NMR spectroscopy
  • boron compounds
  • fluxionality
  • iron complexes
  • rearrangement

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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