Rate and mechanism of the oxidative addition of benzoic anhydride to palladium(0) complexes in DMF

被引：0
|
作者：
Jutand, A
Négri, S
de Vries, JG
机构：
[1] Ecole Normale Super, Dept Chim, UMR CNRS 8640, F-75231 Paris 5, France
[2] Univ Groningen, Lab Organ & Mol Inorgan Chem, NL-9747 AG Groningen, Netherlands
来源：
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2002年 / 07期
关键词：
palladium; kinetics; Electrochemistry; benzoic anhydride; oxidative addition;
D O I：
10.1002/1099-0682(200207)2002:73.0.CO;2-X
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The rate constant of the oxidative addition of the benzoic anhydride (PhCO)(2)O to [Pd-0(PPh3)(4)] has been determined in DMF and compared to that of phenyl halides and phenyl triflate. The following reactivity order has been established: PhI >> (PhCO)(2)O > PhOTf > PhBr. The oxidative addition of (PhCO)(2)O proceeds by activation of one C-O bond. Two acyl-P-II complexes are formed: a neutral complex trans-[(PhCO)Pd(OCOPh)(PPh3)(2)] and a cationic complex trans-[(PhCO)PdS(PPh3)(2)](+) (S = DNIF) showing that the decarbonylation process is highly endergonic, The exchange of PPh3 by the bidentate ligand dppp does not favor the decarbonylation process.
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页码：1711 / 1717
页数：7
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