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

Abstract

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*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 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.