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Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride01:26

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

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Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation...
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Carbocations02:10

Carbocations

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Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...
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Properties of Transition Metals02:58

Properties of Transition Metals

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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.
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Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

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This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
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Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

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The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
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Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

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Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
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Reverse Microemulsion-mediated Synthesis of Monometallic and Bimetallic Early Transition Metal Carbide and Nitride Nanoparticles
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Chemically Stable Group IV-V Transition Metal Carbide Thin Films in Hydrogen Radical Environments.

Abdul Rehman1, Robbert W E van de Kruijs1, Wesley T E van den Beld1

  • 1Industrial Focus Group XUV Optics, MESA+ Institute for Nanotechnology, University of Twente, Drienerlolaan 5, Enschede 7522NB, The Netherlands.

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Transition metal carbide (TMC) thin films show promise as protective coatings in hydrogen environments. Certain TMCs exhibit stable carbidic-carbon content, resisting hydrogen radical attack at high temperatures.

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Area of Science:

  • Materials Science
  • Surface Chemistry
  • Hydrogen Energy

Background:

  • Hydrogen's reactivity and diffusion pose challenges for materials in green energy systems.
  • Protective coatings are essential for components exposed to molecular hydrogen, hydrogen radicals (H*), and plasma.
  • Group IV-V transition metal carbides (TMCs) are investigated for their potential as protective coatings.

Purpose of the Study:

  • To evaluate the stability of various TMC thin films under exposure to hydrogen radicals (H*) at elevated temperatures.
  • To classify TMCs based on their surface reactions and stability in H* environments.
  • To elucidate the mechanisms of H* interaction with TMC surfaces.

Main Methods:

  • Exposure of TiC, ZrC, HfC, VC, NbC, TaC, and Co2C thin films to H* at high temperatures.
  • X-ray photoelectron spectroscopy (XPS) analysis before and after H* exposure.
  • Estimation of thermodynamic energy barriers for surface reactions using Gibbs free energy changes.

Main Results:

  • TMCs were classified into three groups based on their stability and surface deoxidation.
  • HfC, ZrC, TiC, TaC, NbC, and VC (Class A) maintained stable carbidic-carbon content.
  • Co2C (Class B) showed significant carbide reduction and deoxidation.

Conclusions:

  • Class A TMCs, particularly TaC, NbC, and VC, demonstrate superior stability as protective coatings in H* environments.
  • Surface carbidic-carbon hydrogenation limits TMC reduction, while deoxidation is governed by the H2O formation energy barrier.
  • These findings guide the selection of robust materials for hydrogen energy applications.