Amatore C, Jutand A
Département de Chimie, Ecole Normale Supérieure, CNRS UMR 8640, 24 Rue Lhomond, F-75231 Paris Cedex 5, France.
Acc Chem Res. 2000 May;33(5):314-21. doi: 10.1021/ar980063a.
The anions of PdCl(2)L(2) and Pd(OAc)(2), precursors of palladium(0) used in cross-coupling and Heck reactions, play a crucial role in these reactions. Tricoordinated anionic complexes Pd(0)L(2)Cl(-) and Pd(0)L(2)(OAc)(-) are the effective catalysts instead of the usually postulated Pd(0)L(2) complex. The anion ligated to the palladium(0) affects the kinetics of the oxidative addition to ArI as well as the structure and reactivity of the arylpalladium(II) complexes produced in this reaction. Thus, pentacoordinated anionic complexes are formed, ArPdI(Cl)L(2)(-) or ArPdI(OAc)L(2)(-), the precursor of neutral trans-ArPd(OAc)L(2), instead of the usually postulated trans-ArPdIL(2) complex (L = PPh(3)).
用于交叉偶联反应和Heck反应的钯(0)前体PdCl(2)L(2)和Pd(OAc)(2)的阴离子在这些反应中起着至关重要的作用。三配位阴离子配合物Pd(0)L(2)Cl(-)和Pd(0)L(2)(OAc)(-)是有效的催化剂，而非通常假定的Pd(0)L(2)配合物。与钯(0)相连的阴离子会影响对ArI的氧化加成动力学以及该反应中生成的芳基钯(II)配合物的结构和反应活性。因此，形成了五配位阴离子配合物ArPdI(Cl)L(2)(-)或ArPdI(OAc)L(2)(-)，即中性反式-ArPd(OAc)L(2)的前体，而不是通常假定的反式-ArPdIL(2)配合物（L = PPh(3)）。
