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

Open Access
Authors
  • A.A. Danopoulos
  • P. Braunstein
  • K.Y. Monakhov
  • J. van Leusen
  • P. Kögerler
  • M. Clémancey
  • J.-M. Latour
  • A. Benayad
  • M. Tromp
  • E. Rezabal
  • G. Frison
Publication date 28-01-2017
Journal Dalton Transactions
Volume | Issue number 46 | 4
Pages (from-to) 1163-1171
Organisations
  • Faculty of Science (FNWI) - Van 't Hoff Institute for Molecular Sciences (HIMS)
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.
Document type Article
Note With supplementary materials
Language English
Related dataset CCDC 1469264: Experimental Crystal Structure Determination CCDC 1469263: Experimental Crystal Structure Determination CCDC 1469265: Experimental Crystal Structure Determination CCDC 1469268: Experimental Crystal Structure Determination
Published at https://doi.org/10.1039/c6dt03565e
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