ArticleInorganic chemistry2016
Alkali Metal Variation and Twisting of the FeNNFe Core in Bridging Diiron Dinitrogen Complexes.
Article in Inorganic chemistry, 2016. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 14 papers.
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Who cites it
14 citing papers in PubMed.
- Alkali metal cation effects for rapid C-H activation by iron(0) complexes.Chemical science · 2026Article
- Neighboring Alkali Cations as an Efficient Strategy for NInternational journal of molecular sciences · 2026Article
- Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis.Chemical reviews · 2024Review
- Mössbauer and Nuclear Resonance Vibrational Spectroscopy Studies of Iron Species Involved in N-N Bond Cleavage.Inorganic chemistry · 2023Article
- Hydrogen Bonding to a Dinitrogen Complex at Room Temperature: Impacts on NJournal of the American Chemical Society · 2019Article
- Counterion influence on dynamic spin properties in a V(iv) complex.Chemical science · 2019Article
- Isolation and characterization of a high-spin mixed-valent iron dinitrogen complex.Chemical communications (Cambridge, England) · 2018Article
- Alkali Cation Effects on Redox-Active Formazanate Ligands in Iron Chemistry.Inorganic chemistry · 2018Article
- Effects of NJournal of the American Chemical Society · 2018Article
- Reversible Ligand-Centered Reduction in Low-Coordinate Iron Formazanate Complexes.Chemistry (Weinheim an der Bergstrasse, Germany) · 2018Article
- Density Functional Calculations for Prediction ofACS omega · 2017Article
- Coordination chemistry insights into the role of alkali metal promoters in dinitrogen reduction.Catalysis today · 2017Article
- Testing the Push-Pull Hypothesis: Lewis Acid Augmented NJournal of the American Chemical Society · 2017Article
- Molecular titanium nitrides: nucleophiles unleashed.Chemical science · 2017Article
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6 authors.
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Abstract
Alkali metal cations can interact with Fe-N2 complexes, potentially enhancing back-bonding or influencing the geometry of the iron atom. These influences are relevant to large-scale N2 reduction by iron, such as in the FeMoco of nitrogenase and the alkali-promoted Haber-Bosch process. However, to our knowledge there have been no systematic studies of a large range of alkali metals regarding their influence on transition metal-dinitrogen complexes. In this work, we varied the alkali metal in [alkali cation]2[LFeNNFeL] complexes (L = bulky β-diketiminate ligand) through the size range from Na(+) to K(+), Rb(+), and Cs(+). The FeNNFe cores have similar Fe-N and N-N distances and N-N stretching frequencies despite the drastic change in alkali metal cation size. The two diketiminates twist relative to one another, with larger dihedral angles accommodating the larger cations. In order to explain why the twisting has so little influence on the core, we performed density functional theory calculations on a simplified LFeNNFeL model, which show that the two metals surprisingly do not compete for back-bonding to the same π* orbital of N2, even when the ligand planes are parallel. This diiron system can tolerate distortion of the ligand planes through compensating orbital energy changes, and thus, a range of ligand orientations can give very similar energies.
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