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

共 88 条

[1] The geometric and electronic structure of [(cyclam-acetato)Fe(N)+]:: A genuine iron(V) species with a ground-state spin S=1/2 [J].

Aliaga-Alcalde, N ;

George, SD ;

Mienert, B ;

Bill, E ;

Wieghardt, K ;

Neese, F .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (19) :2908-2912

[2] Ammonia formation by metal-ligand cooperative hydrogenolysis of a nitrido ligand [J].

Askevold, Bjorn ;

Nieto, Jorge Torres ;

Tussupbayev, Samat ;

Diefenbach, Martin ;

Herdtweck, Eberhardt ;

Holthausen, Max C. ;

Schneider, Sven .

NATURE CHEMISTRY, 2011, 3 (07) :532-537

[3] Systematically convergent basis sets for transition metals.: I.: All-electron correlation consistent basis sets for the 3d elements Sc-Zn -: art. no. 064107 [J].

Balabanov, NB ;

Peterson, KA .

JOURNAL OF CHEMICAL PHYSICS, 2005, 123 (06)

[4] Basis set limit electronic excitation energies, ionization potentials, and electron affinities for the 3d transition metal atoms:: Coupled cluster and multireference methods [J].

Balabanov, Nikolai B. ;

Peterson, Kirk A. .

JOURNAL OF CHEMICAL PHYSICS, 2006, 125 (07)

[5] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[6] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[7] An octahedral coordination complex of iron(VI) [J].

Berry, John F. ;

Bill, Eckhard ;

Bothe, Eberhard ;

George, Serena DeBeer ;

Mienert, Bernd ;

Neese, Frank ;

Wieghardt, Karl .

SCIENCE, 2006, 312 (5782) :1937-1941

[8] A tetrahedrally coordinated L3Fe-Nx platform that accommodates terminal nitride (FeIVN) and dinitrogen (FeI-N2-FeI) ligands [J].

Betley, TA ;

Peters, JC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (20) :6252-6254

[9] Experimental Definition of the S=1 π vs S=2 σ Reactivity and S=2 Character in the Ground State of an S=1 FeIVO Complex [J].

Braun, Augustin ;

Gee, Leland B. ;

Waters, Max D. J. ;

Baker, Michael L. ;

Mara, Michael W. ;

Zhou, Ang ;

Kroll, Thomas ;

Nordlund, Dennis ;

Sokaras, Dimosthenis ;

Hedman, Britt ;

Hodgson, Keith O. ;

Que Jr, Lawrence ;

Solomon, Edward I. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2024, 146 (51) :35139-35145

[10] Insertion of a metal nitride into carbon-carbon double bonds [J].

Brown, SN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (41) :9752-9753

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