Formation of Ammonia from an Iron Nitrido Complex

Scepaniak, Jeremiah J.; Young, Jessica; Bontchev, Ranko P.; Smith, Jeremy M.

doi:10.1002/ange.200900381

Cited by 61 publications

(22 citation statements)

References 38 publications

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“…The reactive species are challenging to study in technical or biological environments, but various iron nitride complexes have been synthesized in the oxidation states IV, V, and VI to model the possible atomic and electronic structures as well as reaction pathways 3. A variety of ligands was explored which impose four‐, five‐, or six‐coordination on the iron centers with trigonal/tetrahedral,3b,c,e,h, 4 square‐pyramidal,3g and octahedral coordination geometries 3d,f. 5…”

Section: Methodsmentioning

confidence: 99%

“…Tetrahedral Fe IV nitride complexes with bulky trigonal ligands could be synthesized in solution and even isolated 3a. 6 Their reactivity was systematically surveyed for a number of transformations 3h. 6a, 7 The tetrahedral Fe IV nitride groups were found to at least partially decay by intermolecular reductive N–N coupling yielding Fe I ‐NN‐Fe I dimers, provided the steric demand of ligand does not prevent such bimolecular reactions 3e.…”

Section: Methodsmentioning

confidence: 99%

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Decay of Iron(V) Nitride Complexes By a NN Bond‐Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis

2014

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Cryogenically trapped Fe(V) nitride complexes with cyclam-based ligands were found to decay by bimolecular reactions, forming exclusively Fe(II) compounds. Characterization of educts and products by Mössbauer spectroscopy, mass spectrometry, and spectroscopy-oriented DFT calculations showed that the reaction mechanism is reductive nitride coupling and release of dinitrogen (2 Fe(V)≡N→Fe(II)-N=N-Fe(II)→2 Fe(II)+N2). The reaction pathways, representing an "inverse" of the Haber-Bosch reaction, were computationally explored in detail, also to judge the feasibility of yielding catalytically competent Fe(V)(N). Implications for the photolytic cleavage of Fe(III) azides used to generate high-valent Fe nitrides are discussed.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Decay of Iron(V) Nitride Complexes By a NN Bond‐Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis

2014

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“…Da die reaktiven Spezies kaum in ihren technischen oder biologischen Umgebungen zu studieren sind, stellen verschiedenartige Eisenkomplexe, die bisher in den Oxidationsstufen IV, V und VI synthetisiert werden konnten, wichtige Modellverbindungen für die atomare und elektronische Struktur sowie die Reaktivität dar 3. Eine Vielzahl von Liganden wurde dafür erforscht, welche vier‐, fünf‐ und sechsfach koordinierte Eisenzentren in trigonaler/tetraedrischer,3b,c,e,h, 4 quadratisch pyramidaler3g und oktaedrischer Koordination3d,f, 5 lieferten.…”

Section: Methodsunclassified

“…Tetraedrische Nitridoeisen(IV)‐Komplexe mit sterisch anspruchsvollen trigonalen Liganden konnten in Lösung synthetisiert und sogar isoliert werden 3a. 6 Dies ermöglichte es, ihre Reaktivität für verschiedene Umwandlungen systematisch zu studieren 3h. 6a, 7 Dabei wurde auch beobachtet, dass die tetraedrischen Nitridoeisen(IV)‐Komplexe durch intermolekulare reduktive N‐N Kupplung zu Fe I ‐NN‐Fe I ‐Dimeren zerfallen können, wenn der sterische Anspruch der Liganden dies zulässt 3e.…”

Section: Methodsunclassified

Abbau von Nitridoeisen(V)‐Komplexen durch N‐N‐Kupplung in Lösung: spektroskopische und theoretische Analyse

2014

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“…[1][2][3] Many examples have been discovered since the 1965 report [4] of [Ru(NH 3 ) 5 (N 2 )] 2+ . Despite the prominence of iron systems in catalyzing the reduction of dinitrogen in industrial and biological contexts, [1, 2a, 3, 5, 6] and important recent advances in dinitrogen fixation by iron complexes, [1,7] early-and mid-transition metal complexes have shown greatest promise to date in cleaving the NÀN bond. [1][2][3][8][9][10][11] A benchmark was set by Yandulov and Schrock, who reported molybdenum triamidoamine derivatives, the first welldefined catalysts capable of selectively reducing N 2 to ammonia.…”

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Unusually Strong Binding of Dinitrogen to a Ruthenium Center

et al. 2010

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Metal-dinitrogen complexes are of great interest for their potential to reduce energy costs in ammonia production, and to facilitate access to nitrogen-containing organic compounds. [1][2][3] Many examples have been discovered since the 1965 report [4] of [Ru(NH 3 ) 5 (N 2 )] 2+ . Despite the prominence of iron systems in catalyzing the reduction of dinitrogen in industrial and biological contexts, [1, 2a, 3, 5, 6] and important recent advances in dinitrogen fixation by iron complexes, [1,7] early-and mid-transition metal complexes have shown greatest promise to date in cleaving the NÀN bond. [1][2][3][8][9][10][11] A benchmark was set by Yandulov and Schrock, who reported molybdenum triamidoamine derivatives, the first welldefined catalysts capable of selectively reducing N 2 to ammonia.[12] Late-metal complexes tend to be limited by the lower energy of their d orbitals (which impedes back-donation into the high-energy NN antibonding orbitals), [13,14] and high N 2 lability. The latter has been identified as a key barrier to the development of late-metal catalysts for N 2 activation.[2a]Herein we present an experimental and computational study that addresses this barrier.Our interest in the broad catalytic utility of hydridoruthenium complexes of N-heterocyclic carbene (NHC) ligands [15,16] led us to a report from Morris and co-workers describing synthesis of the activated IMes complex 2 (Scheme 1 a; IMes = N,N'-bis(mesityl)imidazol-2-ylidene) through the thermolysis of 1 with excess IMes under argon.[17] We observed a very different reaction chemistry under an atmosphere of dinitrogen:31 P{ 1 H} NMR analysis indicated the formation of less than 10 % of 2 (59.35, 58.72 ppm; ABq, 2 J PP = 13 Hz, THF), but considerable free PPh 3 (Scheme 1 b). The absence of any phosphine ligands in the major product 3 is evident from its null 31 P{ 1 H} NMR spectrum, and from the singlet multiplicity of its hydride signal. This species could be obtained free of 2 by carrying out the reaction at room temperature, and was isolated as an orange powder in 75 % yield by precipitation from hexanes.Single-crystal X-ray analysis of 3 indicated a mononuclear structure containing two mutually trans, unactivated IMes ligands (cf. the activated IMes group present in 2). While disorder impeded the initial assignment of the remaining ligands, we identified 3 as [RuHCl(IMes) 2 (N 2 )] by detailed NMR, IR, and MALDI-TOF mass spectrometric analysis. Refinement of the X-ray data with an appropriate disorder model yields a satisfactory solution. For both complexes in the unit cell, the N 2 and Cl sites are disordered over two positions (as found for other structures containing Cl trans to N 2 ); [18] in one, the hydride is also disordered over two positions. The excellent agreement between the model and the observed data provides unambiguous confirmation of connectivity, although the presence of the disorder limits the discussion of the metrical parameters.The upfield location of the 1 H NMR singlet for the hydride ligand in 3 (À28.03 ppm; C 6 D 6...

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Formation of Ammonia from an Iron Nitrido Complex

Cited by 61 publications

References 38 publications

Decay of Iron(V) Nitride Complexes By a NN Bond‐Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis

Decay of Iron(V) Nitride Complexes By a NN Bond‐Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis

Abbau von Nitridoeisen(V)‐Komplexen durch N‐N‐Kupplung in Lösung: spektroskopische und theoretische Analyse

Unusually Strong Binding of Dinitrogen to a Ruthenium Center

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