Jump to main content
Jump to site search

Issue 1, 2015
Previous Article Next Article

[(η5-C5Me5)Ru]+ fragments ligated to polyaromatic hydrocarbons: an experimental and computational approach to pathways for haptotropic migration

Author affiliations

Abstract

Ligand exchange reactions between [Cp*Ru(NCMe)3][PF6], where Cp* represents η5-C5Me5, and the polycyclic aromatic hydrocarbons (PAHs) pyrene, acenaphthylene and fluoranthene afforded the known [Cp*Ru(η6-pyrene)][PF6] (1) and the new mixed sandwiches [Cp*Ru(η6-acenaphthylene)][PF6] (2) and [Cp*Ru(η6-fluoranthene)][PF6] (3), respectively, isolated in quantitative yields (94–100%). Complex 3 is formed as a mixture of two isomers: 3A as the major product where the [Cp*Ru+] moiety is coordinated to the naphthalene fragment of fluoranthene, and 3B with the coordination of the arenophile to the peripheral benzene ring, in a 90/10 spectroscopic ratio. The composition and identity of the complexes were deduced by elemental analysis, 1H and 13C multidimensional NMR spectroscopy, and mass spectrometry. Compounds 1A, 3A and 2A have been characterized using X-ray structural investigations. That showed that the [Cp*Ru+] unit is η6-attached to one of the two naphthalene rings in each complex. Heating 1 and 3 at 90 °C in CD3NO2 solutions or heating 3 at 120 °C in the solid phase did not provide any evidence for thermally induced intramolecular inter-ring haptotropic rearrangements. These rearrangements were modelled by DFT calculations which indicated rather high activation energies.

Graphical abstract: [(η5-C5Me5)Ru]+ fragments ligated to polyaromatic hydrocarbons: an experimental and computational approach to pathways for haptotropic migration

Back to tab navigation

Supplementary files

Publication details

The article was received on 08 Sep 2014, accepted on 21 Oct 2014 and first published on 22 Oct 2014


Article type: Paper
DOI: 10.1039/C4DT02736A
Author version
available:
Download author version (PDF)
Citation: Dalton Trans., 2015,44, 316-329
  •   Request permissions

    [(η5-C5Me5)Ru]+ fragments ligated to polyaromatic hydrocarbons: an experimental and computational approach to pathways for haptotropic migration

    M. Rioja, P. Hamon, T. Roisnel, S. Sinbandhit, M. Fuentealba, K. Letelier, J. Saillard, A. Vega and J. Hamon, Dalton Trans., 2015, 44, 316
    DOI: 10.1039/C4DT02736A

Search articles by author

Spotlight

Advertisements