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

Molybdän · Photochemie · Radikale · Reaktionsmechanismen · Stickstofffixierung Schema 2. A) Vereinfachte Hückel-Darstellung des Mo-N-N-Mo-p-Systems in 1, 1 + und 1 2+ . B) Photochemische N-N-Spaltung in 1 zur Erzeugung des Nitridokomplexes 2. Die Reduktion von 2 unter sauren Bedingungen führt zur Bildung von NH 3 . Die Oxidation von 2 zu 2 + lçst eine Wasserstoffabstraktion und N-N-Kupplung aus. Schema 3. Radikalische N-N-Kupplung und HAT-Reaktivität von Nitrido-und Nitridylradikalkomplexen.

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Photolytische N₂‐Spaltung: ein Weg zur nachhaltigen NH₃‐Produktion?

Rebreyend

Bruin

2014

Angewandte Chemie

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Spin‐State‐Controlled Photodissociation of Iron(III) Azide to an Iron(V) Nitride Complex

et al. 2017

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We address the generation of the iron(V) nitride complexes, targets of biomimetic chemistry. Temperature dependent ion spectroscopy demonstrate that generation of iron(V) nitrides is governed by the spin state population of their iron(III) azide precursors and can be tuned by temperature. Complex [(MePy2TACN)Fe(N3)] 2+ exists as a mixture of sextet and doublet spin states at 300 K, whereas only the doublet state is populated at 3 K. Photofragmentation of the sextet state complex leads to reduction of the iron center. The doublet state complex photodissociates to the desired iron(V) nitride complex. We show analogous behaviour also for complexes with cyclam-based ligands.

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Conversion of a Fleeting Open‐Shell Iron Nitride into an Iron Nitrosyl

et al. 2019

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Terminal metal nitrides have been proposed as key intermediates in a series of pivotal chemical transformations. However, exploring the chemical activity of transient tetragonal iron(V) nitrides is largely impeded by their facile dimerization in fluid solutions. Herein, in situ EPR and Mössbauer investigations are presented of unprecedented oxygenation of a paramagnetic iron(V) nitrido intermediate, [FeVN(cyclam‐ac)]+ (2, cyclam‐ac−=1,4,8,11‐tetraazacyclotetradecane‐1‐acetate anion), yielding an iron nitrosyl complex, [Fe(NO)(cyclam‐ac)]+ (3). Further theoretical studies suggest that during the reaction a closed‐shell singlet O atom is transferred to 2. Consequently, the N−O bond formation does not follow a radical coupling mechanism proposed for the N−N bond formation but is accomplished by three mutual electron‐transfer pathways between 2 and the O atom donor, thanks to the ambiphilic nature of 2.

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

Abstract: Kryogen abgefangene Fe V

Cited by 9 publications

References 44 publications

Photolytische N₂‐Spaltung: ein Weg zur nachhaltigen NH₃‐Produktion?

Photolytische N₂‐Spaltung: ein Weg zur nachhaltigen NH₃‐Produktion?

Spin‐State‐Controlled Photodissociation of Iron(III) Azide to an Iron(V) Nitride Complex

Conversion of a Fleeting Open‐Shell Iron Nitride into an Iron Nitrosyl

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

Abstract: Kryogen abgefangene Fe V

Cited by 9 publications

References 44 publications

Photolytische N2‐Spaltung: ein Weg zur nachhaltigen NH3‐Produktion?

Photolytische N2‐Spaltung: ein Weg zur nachhaltigen NH3‐Produktion?

Spin‐State‐Controlled Photodissociation of Iron(III) Azide to an Iron(V) Nitride Complex

Conversion of a Fleeting Open‐Shell Iron Nitride into an Iron Nitrosyl

Contact Info

Product

Resources

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Photolytische N₂‐Spaltung: ein Weg zur nachhaltigen NH₃‐Produktion?

Photolytische N₂‐Spaltung: ein Weg zur nachhaltigen NH₃‐Produktion?