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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

Danopoulos, A. A., Braunstein, P., Monakhov, K. Y., van Leusen, J., Koegerler, P., Clemancey, M., Latour, J-M., Benayad, A., Tromp, M., Rezabal, E. & Frison, G., 28-Jan-2017, In : Dalton Transactions. 46, 4, p. 1163-1171 9 p.

Research output: Contribution to journalArticleAcademicpeer-review

  • Andreas A. Danopoulos
  • Pierre Braunstein
  • Kirill Yu. Monakhov
  • Jan van Leusen
  • Paul Koegerler
  • Martin Clemancey
  • Jean-Marc Latour
  • Anass Benayad
  • Moniek Tromp
  • Elixabete Rezabal
  • Gilles Frison

The linear, two-coordinate and isostructural heteroleptic [M(IPr){N(SiMe3)(2)}] (IPr = 1,3-bis(diisopropylphenyl)- imidazol-2-ylidene), formally M-I 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(star)PH(2), mes(star) = 2,4,6-tBu(3)C(6)H(2). The magnetism of 3 and 4 implies Co-II 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 eta(6)-toluene sandwiched between one Fe-0 and one K+ centre.

Original languageEnglish
Pages (from-to)1163-1171
Number of pages9
JournalDalton Transactions
Volume46
Issue number4
Publication statusPublished - 28-Jan-2017
Externally publishedYes

    Keywords

  • HETEROCYCLIC CARBENE COMPLEXES, JAHN-TELLER DISTORTION, HIGH-SPIN IRON(II), AMIDO COMPLEXES, ELECTRONIC-STRUCTURE, LINEAR COORDINATION, ORBITAL MAGNETISM, FREE-ION, LIGANDS, COBALT(II)

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