An Open-Shell FeIV Nitrido

被引：2

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

页码：3174 / 3184

页数：11

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