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Catalysis02:50

Catalysis

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The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
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Precipitation gravimetry is based on converting an analyte into a sparingly soluble precipitate, which is separated by filtration and weighed. An ideal precipitate should be pure, insoluble, of known composition, and easily filtered from the reaction mixture.
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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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Cyanohydrins are formed when cyanide nucleophiles and carbonyl compounds like aldehydes and ketones react. A strong base, the cyanide ion, catalyzes cyanohydrin formation. The ions are generated from HCN under aqueous conditions. Once the cyanide ions are generated, the first step involves the nucleophilic attack of the cyanide ions on the electrophilic carbonyl carbon. This attack shifts the π electrons from the C=O to the oxygen atom forming the alkoxide ion intermediate. The alkoxide anion...
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[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction01:16

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The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
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Cyanohydrins are compounds that contain –CN and –OH groups on the same carbon atom. They are formed by the nucleophilic addition of the cyanide ions to the carbonyl group. Cyanide ions are highly basic and nucleophilic and can be generated from HCN under aqueous conditions. However, since HCN is a weak acid, the number of cyanide ions generated is very small. Hence, a small amount of base or KCN/NaCN is added to HCN to increase the concentration of the cyanide ions in the reaction...
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Closed Synthetic Cycle for Nickel-Based Dihydrogen Formation.

Soosan Hosseinmardi1, Andreas Scheurer1, Frank W Heinemann1

  • 1Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstraße 1, 91058, Erlangen, Germany.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|August 24, 2023
PubMed
Summary

Researchers achieved dihydrogen evolution using a nickel catalyst. A rare nickel dihydrogen complex was identified as a key intermediate in this closed-synthetic cycle.

Keywords:
H2 evolutionNHCnickel complexesnickel dihydrogennickel hydride

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Area of Science:

  • Inorganic Chemistry
  • Catalysis
  • Organometallic Chemistry

Background:

  • Nickel complexes are increasingly studied for catalytic applications.
  • Understanding reaction mechanisms is crucial for catalyst development.
  • Dihydrogen evolution is a key reaction in energy conversion.

Purpose of the Study:

  • To investigate the mechanism of dihydrogen evolution catalyzed by a nickel complex.
  • To identify and characterize key intermediates in the catalytic cycle.
  • To establish a closed-synthetic cycle for dihydrogen evolution.

Main Methods:

  • Synthesis and characterization of nickel complexes.
  • Protonation reactions and isolation of intermediates.
  • Spectroscopic analysis (1H NMR) and gas chromatography.
  • Deuterated acid studies to probe reaction pathways.
  • Density Functional Theory (DFT) calculations.

Main Results:

  • A two-step protonation reaction of a Ni(0) precursor yielded dihydrogen.
  • A Ni(II) monohydride complex was isolated and characterized.
  • A rare nickel dihydrogen complex was detected as a key intermediate.
  • A closed-synthetic cycle was established, regenerating the Ni(0) precursor.

Conclusions:

  • The study elucidates a novel mechanism for dihydrogen evolution involving a nickel dihydrogen intermediate.
  • The findings contribute to the understanding of nickel-catalyzed reactions.
  • This work demonstrates a sustainable catalytic cycle for hydrogen production.