Mechanism of the oxidative carbonylation of terminal alkynes at the ≡C-H bond in solutions of palladium complexes |
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| 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 |
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| Affiliation: | (1) Lomonosov State Academy of Fine Chemical Technology, Moscow, 117571, Russia;(2) Moscow State University, Moscow, 119899, Russia;(3) Karpov Research Institute of Physical Chemistry, Moscow, 103064, Russia;(4) Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, 117813, Russia |
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| 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. |
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