Evidence for an equilibrium between neutral and cationic arylpalladium(II) complexes in DMF. Mechanism of the reduction of cationic arylpalladium(II) complexes

被引：39

作者：

Amatore, C ^{[1
]}

Carre, E ^{[1
]}

Jutand, A ^{[1
]}

机构：

[1] Ecole Normale Super, Dept Chim, CNRS, URA 1679, F-75231 Paris 05, France

来源：

ACTA CHEMICA SCANDINAVICA | 1998年 / 52卷 / 01期

关键词：

D O I：

10.3891/acta.chem.scand.52-0100

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

In DMF, neutral arylpalladium(II) complexes ArPdX(PPh3)(2) (Ar = Ph; X = Cl, Br, I, OAc) are involved in an equilibrium with the cationic complex ArPd(PPh3)(2)(DMF)(+) and the anion X-. The values of the equilibrium constants K-X have been determined and the affinity of X- for ArPd(PPh3)(2)(DMF)(+) is found to be in the order: Cl- > Br- > I- > AcO-. Therefore, albeit the usual reactions with nucleophiles are performed from the neutral complex, the real reactive intermediate might well be the cationic complex. The electrochemical reduction of cationic complexes ArPd(PPh3)(2)(+) affords biaryl, and the mechanism of this reaction has been investigated, It proceeds via transient arylpalladium (I) complexes.

引用

页码：100 / 106

页数：7

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