A Stable Homoleptic Organometallic Iron(IV) Complex

Abstract

A homoleptic organometallic Fe^IV complex that is stable in both solution and in the solid state at ambient conditions has been synthesized and isolated as [Fe(phtmeimb)₂ ](PF₆ )₂ (phtmeimb=[phenyl(tris(3-methylimidazolin-2-ylidene))borate]^- ). This Fe^IV N-heterocyclic carbene (NHC) complex was characterized by ¹ H NMR, HR-MS, elemental analysis, scXRD analysis, electrochemistry, Mößbauer spectroscopy, and magnetic susceptibility. The two latter techniques unequivocally demonstrate that [Fe(phtmeimb)₂ ](PF₆ )₂ is a triplet Fe^IV low-spin S=1 complex in the ground state, in agreement with quantum chemical calculations. The electronic absorption spectrum of [Fe(phtmeimb)₂ ](PF₆ )₂ in acetonitrile shows an intense absorption band in the red and near IR, due to LMCT (ligand-to-metal charge transfer) excitation. For the first time the excited state dynamics of a Fe^IV complex was studied and revealed a ≈0.8 ps lifetime of the ³ LMCT excited state of [Fe(phtmeimb)₂ ](PF₆ )₂ in acetonitrile.