Jump to main content
Jump to site search

Issue 2, 2016
Previous Article Next Article

Mechanistic studies on the addition of hydrogen to iridaepoxide complexes with subsequent elimination of water

Author affiliations

Abstract

Iridium complexes of the PCsp2P ligand in which the donors are linked by 2,3-benzo[b]thiophene groups engage in the cooperative activation of N2O and the resulting iridaepoxides can be treated with dihydrogen to effect elimination of water and regeneration of the starting iridium complex. The mechanism of the steps in this reaction have been investigated using low temperature NMR investigations that reveal H/D exchange processes that point to a highly reactive kinetic product of hydrogen addition to the iridaepoxide. This intermediate is also involved in the water elimination pathway, and model compounds have been synthesized to provide further evidence for the mechanistic proposals for water elimination. The adaptable donor properties of the PCsp2P ligand framework, particularly the anchoring carbene donor, plays a significant role in the ability of these compounds to mediate the transformation of N2O in this way.

Graphical abstract: Mechanistic studies on the addition of hydrogen to iridaepoxide complexes with subsequent elimination of water

Back to tab navigation

Supplementary files

Publication details

The article was received on 21 Sep 2015, accepted on 26 Oct 2015 and first published on 27 Oct 2015


Article type: Edge Article
DOI: 10.1039/C5SC03575A
Chem. Sci., 2016,7, 921-931
  • Open access: Creative Commons BY-NC license
  •   Request permissions

    Mechanistic studies on the addition of hydrogen to iridaepoxide complexes with subsequent elimination of water

    L. E. Doyle, W. E. Piers, J. Borau-Garcia, M. J. Sgro and D. M. Spasyuk, Chem. Sci., 2016, 7, 921
    DOI: 10.1039/C5SC03575A

    This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements