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Heterogeneous Catalysis01:22

Heterogeneous Catalysis

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Heterogeneous catalysis involves a catalyst in a different phase from the reactants. It is a process where the catalyst and the reactants are in distinct phases, typically solid and gas or liquid.Most heterogeneous catalysts are metals, metal oxides, or acids. The list includes transition metals like iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), manganese (Mn), tungsten (W), silver (Ag), and copper (Cu). These metals possess partially vacant d orbitals that...
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Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

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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.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
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Cycloaddition Reactions: Overview01:16

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Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
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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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Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)00:53

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Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
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Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

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Introduction
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Disilametallacyclic chemistry for efficient catalysis.

Yusuke Sunada1, Hideo Nagashima

  • 1Institute for Materials Chemistry and Engineering and CREST, Japan Science and Technology, Kyushu University, Kasuga, Fukuoka 816-8580, Japan. nagasima@cm.kyushu-u.ac.jp.

Dalton Transactions (Cambridge, England : 2003)
|June 14, 2017
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Summary

Disilametallacyclic intermediates enhance organic synthesis catalysis. These intermediates facilitate efficient hydrosilane reduction of carbonyl compounds and alkene hydrogenation via novel mechanisms, advancing catalytic reaction development.

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Area of Science:

  • Organometallic Chemistry
  • Catalysis in Organic Synthesis
  • Silicon-Based Chemistry

Background:

  • Disilametallacyclic compounds are emerging as key players in catalytic transformations.
  • Understanding their reaction mechanisms is crucial for developing efficient synthetic methodologies.

Purpose of the Study:

  • To explore the role of disilametallacyclic intermediates in catalytic reactions.
  • To elucidate novel reaction mechanisms for hydrosilane reduction and alkene hydrogenation.

Main Methods:

  • Experimental and theoretical studies (including DFT calculations) on disilaplatinacycles.
  • Investigation of disilaferra- and disilaruthenacyclic complexes as catalyst precursors.

Main Results:

  • Discovered H2Pt(iv)Si2 species as a highly reactive hydride for amide reduction.
  • Proposed a novel mechanism (σ-CAM) for alkene hydrogenation involving metal-silicon bond activation, bypassing conventional H2 oxidative addition.

Conclusions:

  • Disilametallacyclic intermediates significantly contribute to efficient catalytic reactions.
  • The σ-CAM mechanism offers new insights into transition metal-catalyzed hydrogenations.