Jump to main content
Jump to site search


Tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl metal complexes, [TismPriBenz]M: a new class of metallacarbatranes, isomerization to a tris(N-heterocyclic carbene) derivative, and evidence for an inverted ligand field

Author affiliations

Abstract

The tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl ligand, [TismPriBenz], has been employed to form carbatrane compounds of both the main group metals and transition metals, namely [TismPriBenz]Li, [TismPriBenz]MgMe, [TismPriBenz]Cu and [TismPriBenz]NiBr. In addition to the formation of atranes, a zinc compound that exhibits κ3-coordination, namely [κ3-TismPriBenz]ZnMe, has also been obtained. Furthermore, the [TismPriBenz] ligand may undergo a thermally induced rearrangement to afford a novel tripodal tris(N-heterocyclic carbene) variant, as shown by the conversion of [TismPriBenz]Cu to [κ4-C4-TismPriBenz*]Cu. The transannular M–C bond lengths in the atrane compounds are 0.19–0.32 Å longer than the sum of the respective covalent radii, which is consistent with a bonding description that features a formally zwitterionic component. Interestingly, computational studies demonstrate that the Cu–Catrane interactions in [TismPriBenz]Cu and [κ4-C4-TismPriBenz*]Cu are characterized by an “inverted ligand field”, in which the occupied antibonding orbitals are localized more on carbon than on copper.

Graphical abstract: Tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl metal complexes, [TismPriBenz]M: a new class of metallacarbatranes, isomerization to a tris(N-heterocyclic carbene) derivative, and evidence for an inverted ligand field

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 02 Feb 2017, accepted on 27 Mar 2017 and first published on 02 May 2017


Article type: Edge Article
DOI: 10.1039/C7SC00499K
Citation: Chem. Sci., 2017, Advance Article
  • Open access: Creative Commons BY license
  •   Request permissions

    Tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl metal complexes, [TismPriBenz]M: a new class of metallacarbatranes, isomerization to a tris(N-heterocyclic carbene) derivative, and evidence for an inverted ligand field

    S. Ruccolo, M. Rauch and G. Parkin, Chem. Sci., 2017, Advance Article , DOI: 10.1039/C7SC00499K

    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