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
收藏
页码：3158 / 3160
页数：3
相关论文
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
    Aliaga-Alcalde, N
    George, SD
    Mienert, B
    Bill, E
    Wieghardt, K
    Neese, F
    [J]. 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
    Barney, BM
    Lee, HI
    Dos Santos, PC
    Hoffmann, BM
    Dean, DR
    Seefeldt, LC
    [J]. DALTON TRANSACTIONS, 2006, (19) : 2277 - 2284
  • [4] Synthesis and hydrogenation of bis(imino)pyridine iron Imides
    Bart, SC
    Lobkovsky, E
    Bill, E
    Chirik, PJ
    [J]. 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
    Berry, John F.
    George, Serena DeBeer
    Neese, Frank
    [J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2008, 10 (30) : 4361 - 4374
  • [6] An octahedral coordination complex of iron(VI)
    Berry, John F.
    Bill, Eckhard
    Bothe, Eberhard
    George, Serena DeBeer
    Mienert, Bernd
    Neese, Frank
    Wieghardt, Karl
    [J]. SCIENCE, 2006, 312 (5782) : 1937 - 1941
  • [7] A tetrahedrally coordinated L3Fe-Nx platform that accommodates terminal nitride (FeIVN) and dinitrogen (FeI-N2-FeI) ligands
    Betley, TA
    Peters, JC
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (20) : 6252 - 6254
  • [8] Dinitrogen chemistry from trigonally coordinated iron and cobalt platforms
    Betley, TA
    Peters, JC
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (36) : 10782 - 10783
  • [9] Solvent effects on homolytic bond dissociation energies of hydroxylic acids
    Bordwell, FG
    Liu, WZ
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (44) : 10819 - 10823
  • [10] EQUILIBRIUM ACIDITIES IN DIMETHYL-SULFOXIDE SOLUTION
    BORDWELL, FG
    [J]. ACCOUNTS OF CHEMICAL RESEARCH, 1988, 21 (12) : 456 - 463
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