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Structural Isomerism02:34

Structural Isomerism

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Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly,...
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Stereoisomerism02:52

Stereoisomerism

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Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
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Oxidation and Reduction of Organic Molecules01:19

Oxidation and Reduction of Organic Molecules

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Energy production within a cell involves many coordinated chemical pathways. Most of these pathways are combinations of oxidation and reduction reactions, which occur at the same time. An oxidation reaction strips an electron from an atom in a compound, and the addition of this electron to another compound is a reduction reaction. Because oxidation and reduction usually occur together, these pairs of reactions are called redox reactions.
The removal of an electron from a molecule, results in a...
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Properties of Organometallic Compounds01:23

Properties of Organometallic Compounds

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Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
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Reactions at the Benzylic Position: Oxidation and Reduction00:59

Reactions at the Benzylic Position: Oxidation and Reduction

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The benzylic position describes the position of a carbon atom attached directly to a benzene ring. Benzene by itself does not undergo oxidation. In contrast, the benzylic carbon is quite reactive in the presence of strong oxidizing agents such as KMnO4 or H2CrO4. Therefore, alkylbenzenes are readily oxidized to benzoic acid, irrespective of the type of alkyl groups.
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Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions01:20

Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions

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Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
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Organocopero (III) Complejos de espiro: síntesis, caracterización estructural y transformación redox

Liang Liu1, Miaomiao Zhu1,2, Hai-Tao Yu2

  • 1Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University , Beijing 100871, China.

Journal of the American Chemical Society
|September 22, 2017
PubMed
Resumen

Este estudio proporciona la primera evidencia concreta de los intermediarios de cobre (III) en la formación de enlaces C-C. Se sintetizaron nuevos complejos de espiro de cobre (III) y se demostró su eliminación reductora intramolecular, lo que confirma su papel en la catálisis.

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Área de la Ciencia:

  • Química organometálica
  • Catálisis
  • Química sintética

Sus antecedentes:

  • La eliminación reductora de los intermediarios de cobre es crucial para la formación de enlaces C-C y C-heteroatomo.
  • No hay pruebas directas de estos intermediarios de Cu (III) debido a su inestabilidad.

Objetivo del estudio:

  • Sintetizar y caracterizar estructuralmente los nuevos complejos de espiro de organocopio.
  • Proporcionar pruebas concretas de la participación de los intermediarios de Cu (III) en las reacciones de eliminación reductoras.

Principales métodos:

  • Síntesis de nuevos complejos espiro de organocopio I y organocopio III.
  • Análisis estructural de rayos X monocristalino para determinar las geometrías.
  • Titraciones de redox para observar la interconversión entre los estados Cu ((I) y Cu ((III).

Principales resultados:

  • Se han sintetizado y caracterizado estructuralmente nuevos complejos espiro de organocopio (III) y organocopio (I).
  • El análisis de rayos X reveló geometrías distintas: cuadrado-planar distorsionado para Cu (III) y tetraédrico para Cu (I).
  • Observación experimental de la transformación redox entre los complejos espiro Cu ((I) y Cu ((III).

Conclusiones:

  • Los compuestos de espiro de cobre orgánico sintetizados proporcionan la primera evidencia concreta de los intermediarios de cobre orgánico.
  • Estos complejos Cu (III) se someten a una eliminación reductora intramolecular para formar enlaces C-C.
  • Este trabajo valida el mecanismo propuesto en las reacciones de formación de enlaces catalizados por cobre.