Hertler Phoebe R, Sauza-de la Vega Arturo, Darù Andrea, Sarkar Arup, Lewis Richard A, Wu Guang, Gagliardi Laura, Hayton Trevor W
Department of Chemistry and Biochemistry, University of California Santa Barbara Santa Barbara CA 93106 USA
Department of Chemistry, Pritzker School of Molecular Engineering, James Franck Institute, University of Chicago Chicago IL 60637 USA
Chem Sci. 2024 Sep 10;15(40):16559-66. doi: 10.1039/d4sc04880f.
The reaction of 4 equiv. of Li(N[double bond, length as m-dash]C( Bu)Ph) with FeCl results in isolation of [Li(EtO)][Fe(N[double bond, length as m-dash]C( Bu)Ph)] (1), in good yields. The reaction of 1 with 1 equiv. of I leads to formation of [Fe(N[double bond, length as m-dash]C( Bu)Ph)] (2), in moderate yields. Fe Mössbauer spectroscopy confirms the Fe(iv) oxidation state of 2, and X-ray crystallography reveals that 2 has a square planar coordination geometry along with several intramolecular H⋯C interactions. Furthermore, SQUID magnetometry indicates a small magnetic moment at room temperature, suggestive of an accessible = 1 state. Both density functional theory and multiconfigurational calculations were done to elucidate the nature of the ground state. Consistent with the experimental results, the ground state was found to be an = 0 state with an = 1 excited state close in energy.
4当量的Li(N≡C(t-Bu)Ph)与FeCl反应，能以良好的产率分离得到[Li(EtO)][Fe(N≡C(t-Bu)Ph)]（1）。1与1当量的I反应，以中等产率生成[Fe(N≡C(t-Bu)Ph)]（2）。Fe穆斯堡尔光谱证实了2中Fe的氧化态为Fe(IV)，X射线晶体学表明2具有平面正方形配位几何结构以及若干分子内H⋯C相互作用。此外，超导量子干涉仪磁力测定表明在室温下有一个小的磁矩，这表明存在一个可及的S = 1态。进行了密度泛函理论和多组态计算以阐明基态的性质。与实验结果一致，发现基态为S = 0态，且有一个能量相近的S = 1激发态。
