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Related Concept Videos

¹H NMR: Complex Splitting01:13

¹H NMR: Complex Splitting

2.0K
A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied...
2.0K
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism01:37

1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism

5.1K
Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
5.1K
Interpreting ¹H NMR Signal Splitting: The (n + 1) Rule01:10

Interpreting ¹H NMR Signal Splitting: The (n + 1) Rule

2.8K
In the AX proton spin system, proton A can sense the two spin states of a coupled proton X, resulting in a doublet NMR signal with two peaks of equal (1:1) intensity. When proton A is coupled to two equivalent protons (AX2 spin system), the spin states of each X can be aligned with or against the external field, creating three possible scenarios. This results in a 1:2:1  triplet signal, where the central peak corresponds to the chemical shift of A and is twice as large or intense as the...
2.8K
¹H NMR of Labile Protons: Deuterium (²H) Substitution00:48

¹H NMR of Labile Protons: Deuterium (²H) Substitution

1.4K
This lesson illustrates the role of deuterium substitution in simplifying the NMR spectrum of compounds comprising labile protons. One method employed is the use of deuterium. Amongst the three isotopes of hydrogen, deuterium (2H) has a nucleus composed of one proton and one neutron. When the D2O solvent is added to a pure dry ethanol solution, its labile proton is substituted with deuterium.
1.4K
Electrophilic Aromatic Substitution: Nitration of Benzene01:20

Electrophilic Aromatic Substitution: Nitration of Benzene

9.1K
The nitration of benzene is an example of an electrophilic aromatic substitution reaction. It involves the formation of a very powerful electrophile, the nitronium ion, which is linear in shape. The reaction occurs through the interaction of two strong acids, sulfuric and nitric acid.
9.1K
Nitriles to Carboxylic Acids: Hydrolysis01:08

Nitriles to Carboxylic Acids: Hydrolysis

5.2K
Nitriles undergo acid-catalyzed hydrolysis or base-catalyzed hydrolysis to form a carboxylic acid. These reactions proceed via an amide intermediate.
5.2K

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Measurement of the Potential Rates of Dissimilatory Nitrate Reduction to Ammonium Based on 14NH4+/15NH4+ Analyses via Sequential Conversion to N2O
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Dinitrogen Splitting Coupled to Protonation.

Gleb A Silantyev1, Moritz Förster2, Bastian Schluschaß1

  • 1Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077, Göttingen, Germany.

Angewandte Chemie (International Ed. in English)
|April 25, 2017
PubMed
Summary
This summary is machine-generated.

Researchers discovered a novel method for nitrogen fixation using a molybdenum complex. Protonation on ligand periphery, not the core, drives nitrogen-nitrogen bond cleavage, a key step in converting nitrogen gas into usable forms.

Keywords:
dinitrogenmolybdenumnitrogen fixationpincer ligandprotonation

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Analysis of Complex Molecules and Their Reactions on Surfaces by Means of Cluster-Induced Desorption/Ionization Mass Spectrometry
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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Catalysis
  • Nitrogen Fixation

Background:

  • Controlling redox reactions is crucial for chemical synthesis and energy conversion.
  • Nitrogen fixation, converting atmospheric N2 into ammonia or other nitrogen compounds, is vital for agriculture and industry.
  • Molybdenum complexes are known catalysts for nitrogen reduction, but mechanistic control remains challenging.

Purpose of the Study:

  • To investigate the mechanism of nitrogen (N2) splitting in a molybdenum dinitrogen complex.
  • To understand how coupled electron- and proton-transfer steps influence N-N bond cleavage.
  • To explore the role of ligand structure in controlling the energetics and kinetics of nitrogen fixation.

Main Methods:

  • Spectroscopic analysis (e.g., UV-Vis, NMR) to monitor reaction intermediates and electronic structure changes.
  • Kinetic studies to determine reaction rates and activation parameters.
  • Computational mechanistic analysis (e.g., DFT calculations) to model reaction pathways and energy barriers.

Main Results:

  • Nitrogen-nitrogen (N-N) bond cleavage was achieved in a molybdenum dinitrogen complex.
  • Mechanistic studies revealed that protonation occurs on the periphery of amide pincer ligands, not the central {Mo-N2-Mo} core.
  • This protonation significantly altered the electronic structure, lowering the thermochemistry and kinetic barrier for N-N bond cleavage.

Conclusions:

  • The study demonstrates an unusual proton-coupled metal-to-ligand charge transfer process driving N-N bond cleavage.
  • Proton-responsive ligands offer a new strategy for controlling the driving force and efficiency of nitrogen fixation.
  • This work highlights the potential of ligand design in developing advanced catalysts for nitrogen conversion.