Mechanism of the oxidative carbonylation of terminal alkynes at the ≡C-H bond in solutions of palladium complexes
Mechanism of the oxidative carbonylation of terminal alkynes at the ≡C-H bond in solutions of palladium complexes
复制标题
钯配合物溶液中末端炔烃在≡C-H键处的氧化羰基化机理
DOI：
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发表时间：
2007
期刊：
影响因子：
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通讯作者：
M. Antipin
中科院分区：
文献类型：
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作者：
V. R. Khabibulin;A. Kulik;I. Oshanina;L. Bruk;O. Temkin;V. Nosova;Yury A. Ustynyuk;V. K. Bel’skii;A. Stash;K. A. Lysenko;M. Antipin
本文研究了Pd（OAc）_2-PPh_3-对苯醌（Q）-MeOH催化体系在端炔C-H键氧化羰基化反应中活性催化剂的形成机理。它已被证明由NMR光谱，X-射线晶体学，和动力学测量，催化活性钯是在氧化态0，并结合到由对苯醌（PdL 2 Q，其中L = PPh 3）稳定的配合物。提出了一种催化过程的机理，包括形成络合物PdL 2 Q，炔氧化加成到该络合物的PdC-H键上，CO插入到Pd-C键中，以及氢化物氢分子内转移到对苯醌上的步骤。
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.