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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
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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