An Open-Shell FeIV Nitrido

被引：0
作者：
Oh, Jeewhan [1 ]
Zheng, Shao-Liang [1 ]
Carsch, Kurtis M. [1 ]
Latendresse, Trevor P. [1 ]
Casaday, Claire E. [1 ]
Campbell, Brandon M. [1 ]
Betley, Theodore A. [1 ]
机构：
[1] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2025年 / 147卷 / 04期
基金：
美国国家科学基金会; 美国国家卫生研究院;
关键词：
H BOND AMINATION; NITROGEN-ATOM-TRANSFER; MOSSBAUER ISOMER-SHIFTS; ELECTRONIC-STRUCTURE; BASIS-SETS; SPECTROSCOPIC CHARACTERIZATION; ALKANE HYDROXYLATION; 2-STATE REACTIVITY; CORRELATION-ENERGY; AMMONIA FORMATION;
D O I：
10.1021/jacs.4c12588
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We report the photogeneration and characterization of an open-shell, terminal iron nitrido (EmL)Fe(N) using a sterically encumbered dipyrrin ligand environment. The Fe-N distance in the solid-state, zero-field 57Fe Mossbauer 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 pi*Fe-N enables (i) primary C(sp3)-H amination, (ii) H2 cleavage, (iii) aromatic C-C cleavage, and (iv) photocatalytic N-atom transfer reactivity. These modes of reactivity have not previously been observed in low-spin Fe(N) analogues.
引用
收藏
页码：3174 / 3184
页数：11
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