Oh Jeewhan, Zheng Shao-Liang, Carsch Kurtis M, Latendresse Trevor P, Casaday Claire E, Campbell Brandon M, Betley Theodore A
Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States.
J Am Chem Soc. 2025 Jan 29;147(4):3174-3184. doi: 10.1021/jacs.4c12588. Epub 2025 Jan 19.
We report the photogeneration and characterization of an open-shell, terminal iron nitrido (L)Fe(N) using a sterically encumbered dipyrrin ligand environment. The Fe-N distance in the solid-state, zero-field Fe Mössbauer spectrum, and computational analysis are consistent with a triplet electronic ground state of the iron nitrido. Notably, the attenuation of Fe-N multiple bond character through occupying π* enables (i) primary C(sp)-H amination, (ii) H cleavage, (iii) aromatic C-C cleavage, and (iv) photocatalytic -atom transfer reactivity. These modes of reactivity have not previously been observed in low-spin Fe(N) analogues.
我们报道了使用空间位阻二吡咯配体环境光生并表征了一种开壳层末端铁氮化物（L）Fe（N）。固态中的Fe-N距离、零场Fe穆斯堡尔谱以及计算分析与铁氮化物的三重态电子基态一致。值得注意的是，通过占据π*减弱Fe-N多重键特征能够实现（i）伯C（sp）-H胺化、（ii）H裂解、（iii）芳族C-C裂解以及（iv）光催化-原子转移反应活性。这些反应模式此前在低自旋Fe（N）类似物中尚未观察到。
