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Reduction of Alkenes: Catalytic Hydrogenation02:13

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Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
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Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
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Unlike the easy catalytic hydrogenation of an alkene double bond, hydrogenation of a benzene double bond under similar reaction conditions does not take place easily. For example, in the reduction of stilbene, the benzene ring remains unaffected while the alkene bond gets reduced. Hydrogenation of an alkene double bond is exothermic and a favorable process. In contrast, to hydrogenate the first unsaturated bond of benzene, an energy input is needed; that is, the process is endothermic. This is...
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Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

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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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In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
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Hydrogen Bonds01:04

Hydrogen Bonds

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A hydrogen bond is formed when a weakly positive hydrogen atom already bonded to one electronegative atom (for example, the oxygen in the water molecule) is attracted to another electronegative atom from another polar molecule, such as water (H2O), hydrogen fluoride (HF), or ammonia (NH3). The huge electronegativity difference between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for an N atom), combined with the very small size of an H atom...
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Harnessing the Cobalt-Catalyzed Hydrogen Evolution Reaction through a Data-Driven Approach.

Guangchao Liang1, Min Zhang2

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Summary

This study introduces a data-driven approach (SMADP) to design cobalt complexes for hydrogen evolution reactions (HER). It identifies key descriptors for efficient H2 production, moving beyond trial-and-error methods.

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Area of Science:

  • Catalysis
  • Inorganic Chemistry
  • Materials Science

Background:

  • Cobalt complexes are crucial for hydrogen evolution reactions (HER).
  • Traditional design methods are often inefficient.
  • Developing efficient HER catalysts requires understanding reaction mechanisms.

Purpose of the Study:

  • To introduce a simplified mechanism-based approach with data-driven practice (SMADP) for designing cobalt HER catalysts.
  • To identify active descriptors for cobalt-catalyzed HER.
  • To accelerate the discovery of novel cobalt complexes for enhanced HER.

Main Methods:

  • Application of the SMADP strategy to polypyridyl cobalt complexes.
  • Mechanistic investigation of electron and proton transfer pathways.
  • Identification and regression analysis of active descriptors (ΔGH and ERed°).

Main Results:

  • Polypyridyl cobalt complexes (DPA-Bpy and PY5Me2 families) were studied.
  • Distinct reaction pathways (EC-EC vs. PCET) were observed.
  • Excellent regression models were developed using hydricity (ΔGH) and reduction potential (ERed°) as descriptors.

Conclusions:

  • The SMADP strategy is effective for delineating active descriptors in cobalt-catalyzed HER.
  • Hydricity and reduction potential are key descriptors for H2 formation.
  • This data-driven approach can significantly accelerate the design of advanced HER catalysts.