Jump to main content
Jump to site search


Neutral, cationic and anionic organonickel and -palladium complexes supported by iminophosphine/phosphinoenaminato ligands

Author affiliations

Abstract

We report a series of organometallic nickel and palladium complexes containing iminophosphine ligands R2PCH2C(Ph) = N-Dipp (Dipp = 2,6-diisopropylphenyl; R = iPr, La; R = Ph, Lb; and R = o-C6H4OMe, Lc), synthesized by ligand exchange or oxidative addition reactions, and we investigate the capacity of such ligands to undergo reversible deprotonation to the corresponding phosphinoenaminato species. In the attempted ligand exchange reaction of the nickel bis(trimethylsilyl)methyl precursor [Ni(CH2SiMe3)2Py2] with Lb, the iminophosphine acts as a weak acid rather than a neutral ligand, cleaving one of the Ni–C bonds, to afford the phosphinoenaminato complex [Ni(CH2SiMe3)(L′b)(Py)] (L′b = conjugate base of Lb). We disclose a general method for the syntheses of complexes [Ni(CH2SiMe3)(L)(Py)]+ (L = La, Lb or Lc), and demonstrate that iminophosphine deprotonation is a general feature and occurs reversibly in the coordination sphere of the metal. By studying proton exchange reactions of the cation [Ni(CH2SiMe3)(Lb)(Py)]+ with bases of different strength we show that the conjugate phosphinoenaminato ligand in [Ni(CH2SiMe3)(L′b)(Py)] is a base with strength comparable to DBU in THF. The acyl group in the functionalized aryl complex [Ni(p-C6H4COCH3)(Br)(La)] does not interfere in the iminophosphine deprotonation with NaH. The latter reaction affords the unusual anionic hydroxide species [Ni(p-C6H4COCH3)(OH)(L′a)]Na+, which was isolated and fully characterized.

Graphical abstract: Neutral, cationic and anionic organonickel and -palladium complexes supported by iminophosphine/phosphinoenaminato ligands

Back to tab navigation

Supplementary files

Publication details

The article was received on 17 Oct 2019, accepted on 19 Nov 2019 and first published on 19 Nov 2019


Article type: Paper
DOI: 10.1039/C9DT04062E
Dalton Trans., 2019, Advance Article
  • Open access: Creative Commons BY-NC license
  •   Request permissions

    Neutral, cationic and anionic organonickel and -palladium complexes supported by iminophosphine/phosphinoenaminato ligands

    T. G. Santiago, C. Urbaneja, E. Álvarez, E. Ávila, P. Palma and J. Cámpora, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C9DT04062E

    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