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Nitriles to Amines: LiAlH4 Reduction00:55

Nitriles to Amines: LiAlH4 Reduction

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Nitriles are reduced to amines in the presence of strong reducing agents like lithium aluminum hydride through a typical nucleophilic acyl substitution. The reaction requires two equivalents of the reducing agent. The reducing agent acts as a source of hydride ions.
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
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2° Amines to N-Nitrosamines: Reaction with NaNO201:20

2° Amines to N-Nitrosamines: Reaction with NaNO2

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Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from an aqueous solution of sodium nitrite and strong acids, such as hydrochloric acid or sulfuric acid, in cold conditions. In the presence of an acid, the nitrous acid gets protonated. The subsequent loss of water results in the formation of the electrophile known as nitrosonium ion.
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Properties of Transition Metals02:58

Properties of Transition Metals

26.7K
Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
26.7K
Valence Bond Theory02:42

Valence Bond Theory

9.0K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
9.0K
Preparation of Aldehydes and Ketones from Nitriles and Carboxylic Acids01:24

Preparation of Aldehydes and Ketones from Nitriles and Carboxylic Acids

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Although it is possible to reduce a carboxylic acid to an aldehyde, strong reducing agents, like lithium aluminum hydride (LAH), prohibit a controlled reduction, instead causing the generated aldehyde to instantly over-reduce to a primary alcohol.
Reducing carboxylic acid derivatives like acyl chlorides (RCOCl), esters (RCO2R′), and nitriles (RCN) using milder aluminum hydride agents like lithium tri-tert-butoxyaluminum hydride [LiAlH(O-t-Bu)3] and diisobutylaluminum hydride [DIBAL-H]...
3.6K
meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H01:13

meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H

5.7K
All meta-directing substituents are deactivating groups. These substituents withdraw electrons from the aromatic ring, making the ring less reactive toward electrophilic substitution. For example, the nitration of nitrobenzene is 100,000 times slower than that of benzene because of the deactivating effect of the nitro group. The first step in an electrophilic aromatic substitution is the addition of an electrophile to form a resonance-stabilized carbocation. The energy diagrams for...
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Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
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Two-Dimensional Ordered Double-Transition Metal Carbides for the Electrochemical Nitrogen Reduction Reaction.

Rong Zhao1, Yongting Chen1, Hui Xiang1

  • 1School of Chemistry and Chemical Engineering, Key Laboratory of Hubei Province for Coal Conversion and New Carbon Materials, Wuhan University of Science and Technology, Wuhan430081, China.

ACS Applied Materials & Interfaces
|January 27, 2023
PubMed
Summary

Researchers explored 2D MXenes for electrochemical nitrogen reduction reaction (NRR) catalysis. Mo2Nb2C3 MXene showed excellent activity and selectivity, offering a sustainable alternative to the Haber-Bosch process.

Keywords:
2D materialsDFT calculationsMXenecatalytic mechanismelectrochemistrynitrogen reduction reaction

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Computational Chemistry

Background:

  • The electrochemical nitrogen reduction reaction (NRR) offers a sustainable alternative to the Haber-Bosch process.
  • Developing efficient electrocatalysts for NRR with low overpotential and high selectivity is crucial but challenging.

Purpose of the Study:

  • To computationally screen 18 two-dimensional (2D) ordered double-transition metal carbides (MXenes) for their potential as NRR electrocatalysts.
  • To identify promising MXene materials and understand the underlying mechanisms for high catalytic activity.

Main Methods:

  • Density functional theory (DFT) computations were employed to systematically evaluate the NRR performance of various MXene structures.
  • Calculations focused on adsorption energies, reaction pathways, and overpotentials for NRR and hydrogen evolution reaction (HER).

Main Results:

  • Mo2Nb2C3 MXene demonstrated superior catalytic activity for NRR, with a low overpotential of 0.48 V.
  • This MXene effectively suppressed the competing hydrogen evolution reaction (HER), indicating high selectivity.
  • The Mo3 moiety was identified as key to regulating electron transfer and enhancing catalytic performance.

Conclusions:

  • 2D Mo2Nb2C3 MXene is a highly promising electrocatalyst for the nitrogen reduction reaction.
  • The findings expand the scope of 2D materials for sustainable ammonia synthesis.
  • Computational screening provides a viable strategy for discovering novel NRR electrocatalysts.