Jump to main content
Jump to site search

Issue 2, 2015
Previous Article Next Article

Dehydrogenation of formic acid by Ir–bisMETAMORPhos complexes: experimental and computational insight into the role of a cooperative ligand

Author affiliations

Abstract

The synthesis and tautomeric nature of three xanthene-based bisMETAMORPhos ligands (La–Lc) is reported. Coordination of these bis(sulfonamidophosphines) to Ir(acac)(cod) initially leads to the formation of IrI(LH) species (1a), which convert via formal oxidative addition of the ligand to IrIII(L) monohydride complexes 2a–c. The rate for this step strongly depends on the ligand employed. IrIII complexes 2a–c were applied in the base-free dehydrogenation of formic acid, reaching turnover frequencies of 3090, 877 and 1791 h−1, respectively. The dual role of the ligand in the mechanism of the dehydrogenation reaction was studied by 1H and 31P NMR spectroscopy and DFT calculations. Besides functioning as an internal base, bisMETAMORPhos also assists in the pre-assembly of formic acid within the Ir-coordination sphere and aids in stabilizing the rate-determining transition state through hydrogen-bonding.

Graphical abstract: Dehydrogenation of formic acid by Ir–bisMETAMORPhos complexes: experimental and computational insight into the role of a cooperative ligand

Back to tab navigation

Supplementary files

Publication details

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


Article type: Edge Article
DOI: 10.1039/C4SC02555E
Citation: Chem. Sci., 2015,6, 1027-1034
  • Open access: Creative Commons BY license
  •   Request permissions

    Dehydrogenation of formic acid by Ir–bisMETAMORPhos complexes: experimental and computational insight into the role of a cooperative ligand

    S. Oldenhof, M. Lutz, B. de Bruin, J. Ivar van der Vlugt and J. N. H. Reek, Chem. Sci., 2015, 6, 1027
    DOI: 10.1039/C4SC02555E

    This article is licensed under a Creative Commons Attribution 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.

    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