Formation of Ammonia from an Iron Nitrido Complex

被引：176

作者：

Scepaniak, Jeremiah J. ^{[1
]}

Young, Jessica A. ^{[1
]}

Bontchev, Ranko P. ^{[2
]}

Smith, Jeremy M. ^{[1
]}

机构：

[1] New Mexico State Univ, Dept Chem & Biochem, Las Cruces, NM 88011 USA

[2] New Mexico State Univ, Dept Chem & Biochem, Las Cruces, NM 88011 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2009年 / 48卷 / 17期

关键词：

iron; nitrides; radicals; reaction mechanisms; tripodal ligands; BOND-DISSOCIATION ENERGIES; HYDROGEN-ATOM ABSTRACTION; SPECTROSCOPIC CHARACTERIZATION; GAS-PHASE; FE-IVN; DINITROGEN; MOLYBDENUM; REDUCTION; CHEMISTRY; LIGAND;

D O I：

10.1002/anie.200900381

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Radical ideas: Reaction of the iron(IV) nitrido complex [PhB(MesIm) 3Fe≡N] (see picture, Mes=2,4,6-Me3C 6H2) with TEMPO-H (1-hydroxy-2,2,6,6- tetramethylpiperidine) results in high yields of ammonia and quantitative formation of [PhB(MesIm)3Fe(tempo)]. The mechanism likely involves hydrogen-atom transfer from TEMPO-H to the nitrido complex. Similar reaction with the triphenylmethyl radical yields [PhB(MesIm)3Fe≡N-CPh3]. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：3158 / 3160

页数：3

共 38 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]

Aliaga-Alcalde N., 2005, ANGEW CHEM, V117, P2968

[3] Breaking the N2 triple bond:: insights into the nitrogenase mechanism [J].

Barney, BM ;

Lee, HI ;

Dos Santos, PC ;

Hoffmann, BM ;

Dean, DR ;

Seefeldt, LC .

DALTON TRANSACTIONS, 2006, (19) :2277-2284

[4] Synthesis and hydrogenation of bis(imino)pyridine iron Imides [J].

Bart, SC ;

Lobkovsky, E ;

Bill, E ;

Chirik, PJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (16) :5302-5303

[5] Electronic structure and spectroscopy of "superoxidized" iron centers in model systems: theoretical and experimental trends [J].

Berry, John F. ;

George, Serena DeBeer ;

Neese, Frank .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2008, 10 (30) :4361-4374

[6] 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

[7] 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

[8] Dinitrogen chemistry from trigonally coordinated iron and cobalt platforms [J].

Betley, TA ;

Peters, JC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (36) :10782-10783

[9] Solvent effects on homolytic bond dissociation energies of hydroxylic acids [J].

Bordwell, FG ;

Liu, WZ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (44) :10819-10823

[10] EQUILIBRIUM ACIDITIES IN DIMETHYL-SULFOXIDE SOLUTION [J].

BORDWELL, FG .

ACCOUNTS OF CHEMICAL RESEARCH, 1988, 21 (12) :456-463

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