Jump to main content
Jump to site search

Issue 42, 2016
Previous Article Next Article

Synthesis, structure and reactivity of Pd and Ir complexes based on new lutidine-derived NHC/phosphine mixed pincer ligands

Author affiliations

Abstract

Coordination studies of new lutidine-derived hybrid NHC/phosphine ligands (CNP) to Pd and Ir have been performed. Treatment of the square-planar [Pd(CNP)Cl](AgCl2) complex 2a with KHMDS produces the selective deprotonation at the CH2P arm of the pincer to yield the pyridine-dearomatised complex 3a. A series of cationic [Ir(CNP)(cod)]+ complexes 4 has been prepared by reaction of the imidazolium salts 1 with Ir(acac)(cod). These derivatives exhibit in the solid state, and in solution, a distorted trigonal bipyramidal structure in which the CNP ligands adopt an unusual C(axial)–N(equatorial)–P(equatorial) coordination mode. Reactions of complexes 4 with CO and H2 yield the carbonyl species 5a(Cl) and 6a(Cl), and the dihydrido derivatives 7, respectively. Furthermore, upon reaction of complex 4b(Br) with base, selective deprotonation at the methylene CH2P arms is observed. The, thus formed, deprotonated Ir complex 8b reacts with H2 in a ligand-assisted process leading to the trihydrido complex 9b, which can also be obtained by reaction of 7b(Cl) with H2 in the presence of KOtBu. Finally, the catalytic activity of Ir–CNP complexes in the hydrogenation of ketones has been briefly assessed.

Graphical abstract: Synthesis, structure and reactivity of Pd and Ir complexes based on new lutidine-derived NHC/phosphine mixed pincer ligands

Back to tab navigation

Supplementary files

Publication details

The article was received on 20 Sep 2016, accepted on 27 Sep 2016 and first published on 27 Sep 2016


Article type: Paper
DOI: 10.1039/C6DT03652J
Citation: Dalton Trans., 2016,45, 16997-17009
  • Open access: Creative Commons BY-NC license
  •   Request permissions

    Synthesis, structure and reactivity of Pd and Ir complexes based on new lutidine-derived NHC/phosphine mixed pincer ligands

    P. Sánchez, M. Hernández-Juárez, E. Álvarez, M. Paneque, N. Rendón and A. Suárez, Dalton Trans., 2016, 45, 16997
    DOI: 10.1039/C6DT03652J

    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