Jump to main content
Jump to site search
Publishing
Advanced

Issue 7, 1981
Previous Article Next Article

Paramagnetic carbenemetal complexes. Part 2. Synthesis and spectroscopic studies of stable electron-rich olefin-derived paramagnetic carbenecarbonyl- and carbenenitrosyl-iron(I) complexes

Michael F. Lappert,  Jonathan J. MacQuitty  and  Peter L. Pye 

Abstract

The synthesis of some new electron-rich olefin-derived carbeneiron(0) complexes (1)–(11) of the type [Fe(CO)3(LMe)L′][LMe= C[graphic omitted]Me; L′= PMePh2, PEt2Ph, PPh2H, PPh3, AsPh3, P(C6H11)3, or P (OPh)3], [{Fe(CO)3(LMe)}2(µ-dppe)], (8), and [Fe2(CO)6(LMe)(dppe)] is described, from the appropriate ligand with [Fe(CO)4(LMe)]. These complexes have then been used to produce paramagnetic carbeneiron(I) salts (12)–(38) by one-electron oxidation, generally by use of Ag[BF4]. The iron (I) salts are often chemically and thermally stable, nine examples, e.g.[Fe(CO)3(LMe)2][BF4], being fully characterised as crystalline materials. Oxidation of complex (8) yields the novel di-iron(I) dication [{Fe(CO)3(LMe)}2(µ-dppe)]2+ which contains two independent, non-interacting, low-spin d7 iron atoms. The tricarbonyliron(I) complexes react with various neutral ligands to afford [Fe(CO)2(LMe)(L′)L″]+ cations and CO; such reactions are often followed by disproportionation, e.g.[Fe(CO)3(LMe)(PPh3)]+ gives [Fe(CO)2(LMe)(PPh3)2]+ and [Fe(CO)4(LMe)]+, which may have synthetic utility. The ligand LMe assists stabilisation of the cationic iron(I) state by delocalising positive charge. Infrared and e.s.r. data provide an insight into the structure and stereochemistry of the iron(0)(trigonal-bipyramidal) and iron(I)(distorted square-pyramidal) complexes and suggest that the LMe ligand is a better acceptor of the unpaired electron density than a tertiary phosphine.

Back to tab navigation
Download options Please wait...

Article type: Paper
DOI: 10.1039/DT9810001583
Citation: J. Chem. Soc., Dalton Trans., 1981,0, 1583-1592
  •   Request permissions

    Paramagnetic carbenemetal complexes. Part 2. Synthesis and spectroscopic studies of stable electron-rich olefin-derived paramagnetic carbenecarbonyl- and carbenenitrosyl-iron(I) complexes

    M. F. Lappert, J. J. MacQuitty and P. L. Pye, J. Chem. Soc., Dalton Trans., 1981, 0, 1583
    DOI: 10.1039/DT9810001583

    If you are not the author of this article and you wish to reproduce material from it in a third party non-RSC publication you must formally request permission using RightsLink. Go to our Instructions for using RightsLink page for details.

    Authors contributing to RSC publications (journal articles, books or book chapters) do not need to formally request permission to reproduce material contained in this article provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      Reproduced from Ref. XX with permission from the Centre National de la Recherche Scientifique (CNRS) and The Royal Society of Chemistry.
    • For reproduction of material from PCCP:
      Reproduced from Ref. XX with permission from the PCCP Owner Societies.
    • For reproduction of material from PPS:
      Reproduced from Ref. XX with permission from the European Society for Photobiology, the European Photochemistry Association, and The Royal Society of Chemistry.
    • For reproduction of material from all other RSC journals and books:
      Reproduced from Ref. XX with permission from The Royal Society of Chemistry.

    If the material has been adapted instead of reproduced from the original RSC publication "Reproduced from" can be substituted with "Adapted from".

    In all cases the Ref. XX is the XXth reference in the list of references.

    If you are the author of this article you do not need to formally request permission to reproduce figures, diagrams etc. contained in this article in third party publications or in a thesis or dissertation 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] - Reproduced by permission of 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] - Reproduced by permission of the PCCP Owner Societies
    • For reproduction of material from PPS:
      [Original citation] - Reproduced by permission of 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] - Reproduced by permission of The Royal Society of Chemistry

    If you are the author of this article you still need to obtain permission to reproduce the whole article in a third party publication with the exception of reproduction of the whole article in a thesis or dissertation.

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

Search articles by author

Spotlight

Advertisements