Rate and mechanism of the oxidative addition of vinyl triflates and halides to palladium(0) complexes in DMF
Rate and mechanism of the oxidative addition of vinyl triflates and halides to palladium(0) complexes in DMF
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DOI：
10.1021/om030298c
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发表时间：
2003-10-13
期刊：
影响因子：
2.8
通讯作者：
Négri, S
中科院分区：
文献类型：
--
作者：
Jutand, A;Négri, S
In a coordinating solvent such as DMF, the fast oxidative addition of vinyl triflates to Pd-0(PPh3)(4) performed under stoichiometric conditions gives the cationic complexes [(eta(1)-vinyl)Pd(PPh3)(2)(DMF)]+TfO-, which have been characterized by conductivity measurements, electrospray mass spectrometry, and NMR spectroscopy, before their decomposition to vinylphosphonium salts [vinyl-PPh3]+TfO- and Pd-0 complexes. [(eta(1)-vinyl)Pd(PPh3)(2)(DMF)]+TfO- complexes are less stable than [(aryl)Pd(PPh3)(2)(DMF)]+TfO- formed in the oxidative addition of aryl triflates to Pd-0(PPh3)(4). The rate constant of the oxidative addition of vinyl triflates and bromides to Pd-0(PPh3)(4) has been determined and compared to that of aryl triflates and halides. The following reactivity orders are established in DMF: vinyl-OTf much greater than vinyl-Br > PhBr and vinyl-OTf much greater than PhOTf.
