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Literature DB >> 25394570

Low-temperature N2 binding to two-coordinate L2Fe(0) enables reductive trapping of L2FeN2(-) and NH3 generation.

Abstract

The two-coordinate [(CAAC)2Fe] complex [CAAC = cyclic (alkyl)(amino)carbene] binds dinitrogen at low temperature (T<-80 °C). The resulting putative three-coordinate N2 complex, [(CAAC)2Fe(N2)], was trapped by one-electron reduction to its corresponding anion [(CAAC)2FeN2](-) at low temperature. This complex was structurally characterized and features an activated dinitrogen unit which can be silylated at the β-nitrogen atom. The redox-linked complexes [(CAAC)2Fe(I)][BAr(F)4], [(CAAC)2Fe(0)], and [(CAAC)2Fe(-I)N2](-) were all found to be active for the reduction of dinitrogen to ammonia upon treatment with KC8 and HBAr(F)4⋅2 Et2O at -95 °C [up to (3.4±1.0) equivalents of ammonia per Fe center]. The N2 reduction activity is highly temperature dependent, with significant N2 reduction to NH3 only occurring below -78 °C. This reactivity profile tracks with the low temperatures needed for N2 binding and an otherwise unavailable electron-transfer step to generate reactive [(CAAC)2FeN2](-) .

Entities: Chemical Disease Gene Species

Keywords: carbenes; coordination modes; iron; nitrogen fixation; structure elucidation

Mesh：

Substances：
Ferric Compounds
Ammonia

Year: 2014 PMID： 25394570 PMCID： PMC4314396 DOI： 10.1002/anie.201409454

Source DB: PubMed Journal: Angew Chem Int Ed Engl ISSN： 1433-7851 Impact factor: 15.336

27 in total

1. Molecular N2 complexes of iron stabilised by N-heterocyclic 'pincer' dicarbene ligands.

Authors: Andreas A Danopoulos; Joseph A Wright; William B Motherwell
Journal: Chem Commun (Camb) Date: 2004-12-22 Impact factor: 6.222

2. Catalytic reduction of N2 to NH3 by an Fe-N2 complex featuring a C-atom anchor.

Authors: Sidney E Creutz; Jonas C Peters
Journal: J Am Chem Soc Date: 2014-01-09 Impact factor: 15.419

3. Molybdenum-catalyzed transformation of molecular dinitrogen into silylamine: experimental and DFT study on the remarkable role of ferrocenyldiphosphine ligands.

Authors: Hiromasa Tanaka; Akira Sasada; Tomohisa Kouno; Masahiro Yuki; Yoshihiro Miyake; Haruyuki Nakanishi; Yoshiaki Nishibayashi; Kazunari Yoshizawa
Journal: J Am Chem Soc Date: 2011-02-22 Impact factor: 15.419

Low-temperature N2 binding to two-coordinate L2Fe(0) enables reductive trapping of L2FeN2(-) and NH3 generation.

1. Molecular N2 complexes of iron stabilised by N-heterocyclic 'pincer' dicarbene ligands.

2. Catalytic reduction of N2 to NH3 by an Fe-N2 complex featuring a C-atom anchor.

3. Molybdenum-catalyzed transformation of molecular dinitrogen into silylamine: experimental and DFT study on the remarkable role of ferrocenyldiphosphine ligands.

4. Molybdenum-catalyzed reduction of molecular dinitrogen under mild reaction conditions.

5. A molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia.

6. Fe-N2/CO complexes that model a possible role for the interstitial C atom of FeMo-cofactor (FeMoco).

7. Cobalt-Magnesium and Iron-Magnesium Complexes with Weakened Dinitrogen Bridges.

8. Iron-catalysed transformation of molecular dinitrogen into silylamine under ambient conditions.

9. Dinitrogen chemistry from trigonally coordinated iron and cobalt platforms.

10. Catalytic conversion of nitrogen to ammonia by an iron model complex.

Review 1. Catalytic N₂-to-NH₃ (or -N₂H₄) Conversion by Well-Defined Molecular Coordination Complexes.

2. N-H Bond Dissociation Enthalpies and Facile H Atom Transfers for Early Intermediates of Fe-N₂ and Fe-CN Reductions.

3. Effects of N₂ Binding Mode on Iron-Based Functionalization of Dinitrogen to Form an Iron(III) Hydrazido Complex.

4. Evaluating molecular cobalt complexes for the conversion of N2 to NH3.

5. Characterization of an Fe≡N-NH2 Intermediate Relevant to Catalytic N2 Reduction to NH3.

6. Light Enhanced Fe-Mediated Nitrogen Fixation: Mechanistic Insights Regarding H₂ Elimination, HER, and NH₃ Generation.

7. Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes.

8. Coordination chemistry insights into the role of alkali metal promoters in dinitrogen reduction.

9. Evaluating Metal Ion Identity on Catalytic Silylation of Dinitrogen Using a Series of Trimetallic Complexes.

10. Ta₂ ⁺-mediated ammonia synthesis from N₂ and H₂ at ambient temperature.

Review 1. Catalytic N2-to-NH3 (or -N2H4) Conversion by Well-Defined Molecular Coordination Complexes.

Review 1. Catalytic N₂-to-NH₃ (or -N₂H₄) Conversion by Well-Defined Molecular Coordination Complexes.