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Issue 4, 2017
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Heteroleptic, two-coordinate [M(NHC){N(SiMe3)2}] (M = Co, Fe) complexes: synthesis, reactivity and magnetism rationalized by an unexpected metal oxidation state

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Abstract

The linear, two-coordinate and isostructural heteroleptic [M(IPr){N(SiMe3)2}] (IPr = 1,3-bis(diisopropylphenyl)-imidazol-2-ylidene), formally MI complexes (M = Co, 3; Fe, 4) were obtained by the reduction of [M(IPr)Cl{N(SiMe3)2}] with KC8, or [Co(IPr){N(SiMe3)2}2] with mes*PH2, mes* = 2,4,6-tBu3C6H2. The magnetism of 3 and 4 implies CoII and FeII centres coupled to one ligand-delocalized electron, in line with XPS and XANES data; the ac susceptibility of 4 detected a pronounced frequency dependence due to slow magnetization relaxation. Reduction of [Fe(IPr)Cl{N(SiMe3)2}] with excess KC8 in toluene gave the heteronuclear ‘inverse-sandwich’ Fe–K complex 7, featuring η6-toluene sandwiched between one Fe0 and one K+ centre.

Graphical abstract: Heteroleptic, two-coordinate [M(NHC){N(SiMe3)2}] (M = Co, Fe) complexes: synthesis, reactivity and magnetism rationalized by an unexpected metal oxidation state

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Publication details

The article was received on 13 Sep 2016, accepted on 20 Dec 2016 and first published on 21 Dec 2016


Article type: Paper
DOI: 10.1039/C6DT03565E
Citation: Dalton Trans., 2017,46, 1163-1171
  • Open access: Creative Commons BY-NC license
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    Heteroleptic, two-coordinate [M(NHC){N(SiMe3)2}] (M = Co, Fe) complexes: synthesis, reactivity and magnetism rationalized by an unexpected metal oxidation state

    A. A. Danopoulos, P. Braunstein, K. Yu. Monakhov, J. van Leusen, P. Kögerler, M. Clémancey, J. Latour, A. Benayad, M. Tromp, E. Rezabal and G. Frison, Dalton Trans., 2017, 46, 1163
    DOI: 10.1039/C6DT03565E

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