Jump to main content
Jump to site search


A general benzylic C–H activation and C–C coupling reaction of zirconocenes mediated by C–N bond cleavage in tert-butylisocyanide – unusual formation of iminoacyl complexes

Author affiliations

Abstract

Reactions of the zirconocene alkyne complex [rac-(ebthi)Zr(η2-Me3SiC2SiMe3)] (rac-(ebthi) = rac-1,2-ethylene-1,1′-bis(η5-tetrahydroindenyl)) with tert-butylisocyanide and methylbenzenes were investigated. Depending on the stoichiometry, the solvent and the reaction temperature different products were obtained. Starting with the end-on coordination of the isocyanide to the zirconium centre (2), elevated reaction temperatures and an excess of tert-butylisocyanide resulted after the elimination of the alkyne in the formation of zirconocene η2-iminoacyl cyanide complexes 3a–d. These complexes are formed by coupling with a benzyl fragment through C–H bond activation of a methyl group of methylbenzene. The dimeric cyanide bridged zirconocene complex 4 is formed as a side-product of this process. The unexpected dimer and the heterometallacycles were fully characterised, including X-ray crystallography.

Graphical abstract: A general benzylic C–H activation and C–C coupling reaction of zirconocenes mediated by C–N bond cleavage in tert-butylisocyanide – unusual formation of iminoacyl complexes

Back to tab navigation

Supplementary files

Publication details

The article was received on 31 Jul 2019, accepted on 30 Sep 2019 and first published on 01 Oct 2019


Article type: Paper
DOI: 10.1039/C9DT03120K
Dalton Trans., 2019, Advance Article

  •   Request permissions

    A general benzylic C–H activation and C–C coupling reaction of zirconocenes mediated by C–N bond cleavage in tert-butylisocyanide – unusual formation of iminoacyl complexes

    P. Arndt, M. Reiß, A. Spannenberg, C. Schünemann, F. Reiß and T. Beweries, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C9DT03120K

Search articles by author

Spotlight

Advertisements