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Royal Society of Chemistry, Dalton Transactions, 4(46), p. 1163-1171

DOI: 10.1039/c6dt03565e

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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

Journal article published in 2017 by Andreas A. Danopoulos, Pierre Braunstein ORCID, Kirill Y.-U. Monakhov, Jan Van Leusen, Paul Kögerler ORCID, Martin Clémancey, Jean-Marc Latour, Anass Benayad, Gilles Frison, Moniek Tromp, Elixabete Rezabal
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

The linear, two-coordinate and isostructural heteroleptic [M(IPr){N(SiMe3)2}] (IPr = 1,3-bis(diisopropyl-phenyl)-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*PH2, mes* = 2,4,6-tBu3C6H2. The magnetism of 3 and 4 implies Co(II) and Fe(II) 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 magnetiza-tion relaxation. Reduction of [Fe(IPr)Cl{N(SiMe 3)2}] with excess KC 8 in toluene gave the heteronuclear 'inverse-sandwich' Fe–K complex 7, featuring 6-toluene sandwiched between one Fe(0) and one K(+) centre.