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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| Institution: | (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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