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- Title
Mechanism of the oxidative carbonylation of terminal alkynes at the ≡C-H bond in solutions of palladium complexes.
- Authors
Khabibulin, V. R.; Kulik, A. V.; Oshanina, I. V.; Bruk, L. G.; Temkin, O. N.; Nosova, V. M.; Ustynyuk, Yu. A.; Bel'skii, V. K.; Stash, A. I.; Lysenko, K. A.; Antipin, M. Yu.
- 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.
- Subjects
CATALYSTS; NUCLEAR magnetic resonance spectroscopy; X-ray crystallography; PALLADIUM; ALKYNES; HYDROGEN
- Publication
Kinetics & Catalysis, 2007, Vol 48, Issue 2, p228
- ISSN
0023-1584
- Publication type
Article
- DOI
10.1134/S0023158407020073