Mechanism of the oxidative carbonylation of terminal alkynes at the ≡C-H bond in solutions of palladium complexes View Full Text


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

2007-03

AUTHORS

V. R. Khabibulin, A. V. Kulik, I. V. Oshanina, L. G. Bruk, O. N. Temkin, V. M. Nosova, Yu. A. Ustynyuk, V. K. Bel’skii, A. I. Stash, K. A. Lysenko, M. Yu. Antipin

ABSTRACT

The formation mechanism of the active catalyst in the oxidative carbonylation of terminal alkynes at the ≡C-H bond has been investigated for the catalytic system Pd(OAc)2-PPh3-p-benzoquinone (Q)-MeOH. It has been demonstrated by NMR spectroscopy, X-ray crystallography, and kinetic measurements that the catalytically active palladium is in the oxidation state 0 and is bound into complexes stabilized by p-benzoquinone (PdL2Q, where L = PPh3). A mechanism is suggested for the catalytic process, which includes the formation of the complex PdL2Q, the oxidative addition of the alkyne to this complex at the ≡C-H bond, the insertion of CO into the Pd-C bond, and steps in which hydride hydrogen is intramolecularly transferred to the p-quinone. More... »

PAGES

228-244

Identifiers

URI

http://scigraph.springernature.com/pub.10.1134/s0023158407020073

DOI

http://dx.doi.org/10.1134/s0023158407020073

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1041336275


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