Direct Spectroscopic Observation of Large Quenching of First-Order Orbital Angular Momentum with Bending in Monomeric, Two-Coordinate Fe(ll) Primary Amido Complexes and the Profound Magnetic Effects of the Absence of Jahn- and Renner-Teller Distortions in Rigorously Linear Coordination

摘要

The monomeric iron(ll) amido derivatives Fe{N(H)Ar*}_2 (1), Ar* = C_6U_3-2,6-(C_6H_2-2,4,6-Pr_3~i)_2, and Fe{N(H)Ar#}_2 (2), Ar# = C_6H_3-2,6-(C_6H_2-2,4,6-Me_3)_2, were synthesized and studied in order to determine the effects of geometric changes on their unusual magnetic properties. The compounds, which are the first stable homoleptic primary amides of iron(ll), were obtained by the transamination of Fe{N(SiMe_3)_2}_2, with HN(SiMe_3)_2 elimination, by the primary amines H_2NAr* or H_2NAr#. X-ray crystallography showed that they have either strictly linear (1) or bent (2, N-Fe-N = 140.9(2)°) iron coordination. Variable temperature magnetization and applied magnetic field Mossbauer spectroscopy studies revealed a very large dependence of the magnetic properties on the metal coordination geometry. At ambient temperature, the linear 1 displayed an effective magnetic moment in the range 7.0-7.50 μ_B, consistent with essentially free ion magnetism. There is a very high internal orbital field component, H_L ≈ 170 T which is only exceeded by a H_L≈ 203 T of Fe{C(SiMe_3)_3}_2. In contrast, the strongly bent 2 displayed a significantly lower μ_(eff) value in the range 5.25-5.80 μ_B at ambient temperature and a much lower orbital field H_L value of 116 T. The data for the two amido complexes demonstrate a very large quenching of the orbital magnetic moment upon bending the linear geometry. In addition, a strong correlation of H_L with overall formal symmetry is confirmed. ESR spectroscopy supports the existence of large orbital magnetic moments in 1 and 2, and DFT calculations provide good agreement with the physical data.