Publication

Why are (NN2)Ni pincer complexes active for alkyl-alkyl coupling: ß-H elimination is kinetically accessible but thermodynamically uphill

Rosario Scopelliti, Xile Hu, Anne-Clémence Corminboeuf, Oleg Vechorkin, Jan Breitenfeld
2010
Journal Articles

Résumé

Isomerization and olefin exchange experiments show that β-H elimination is kinetically viable but thermodynamically unfavorable in [(MeNN2)Ni-alkyl] complexes. The intermediacy of Ni-hydride species was corroborated by a trapping experiment. The alkyl complex [(MeNN2)Ni-propyl] catalyzes olefin isomerization.

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https://infoscience.epfl.ch/entities/publication/82288f77-6648-4d36-887a-dcf3559406db

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Rosario Scopelliti, Xile Hu, Anne-Clémence Corminboeuf, Oleg Vechorkin, Jan Breitenfeld
2010
Journal Articles

Résumé

Source officielle

https://infoscience.epfl.ch/entities/publication/82288f77-6648-4d36-887a-dcf3559406db

À propos de ce résultat

Concepts associés (8)

Isomerization

In chemistry, isomerization or isomerisation is the process in which a molecule, polyatomic ion or molecular fragment is transformed into an isomer with a different chemical structure. Enolization is an example of isomerization, as is tautomerization. When the isomerization occurs intramolecularly it may be called a rearrangement reaction. When the activation energy for the isomerization reaction is sufficiently small, both isomers will exist in a temperature-dependent equilibrium with each other.

Procédé Wacker

Le procédé Wacker ou le procédé Hoechst-Wacker (nommé d'après les entreprises chimiques du même nom) est un procédé industriel de type chimique. Il se réfère à l'oxydation de l'éthylène en acétaldéhyde en présence de chlorure de palladium(II) comme catalyseur. Cette réaction chimique a été l'une des premières catalyses homogènes avec un organopalladium appliquée à une échelle industrielle. Le développement du procédé Wacker commence en 1956, à la société Wacker Chemie.

Enolate

In organic chemistry, enolates are organic anions derived from the deprotonation of carbonyl () compounds. Rarely isolated, they are widely used as reagents in the synthesis of organic compounds. Enolate anions are electronically related to allyl anions. The anionic charge is delocalized over the oxygen and the two carbon sites. Thus they have the character of both an alkoxide and a carbanion. Although they are often drawn as being simple salts, in fact they adopt complicated structures often featuring aggregates.

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Publications associées (7)

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Why are (NN2)Ni pincer complexes active for alkyl-alkyl coupling: ß-H elimination is kinetically accessible but thermodynamically uphill

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