Kinetic Data on the Synergetic Role of Amines and Water in the Reduction of Phosphine-Ligated Palladium(II) to Palladium(0)

被引：24

作者：

Amatore, Christian ^{[1
]}

El Kaim, Laurent ^{[2
]}

Grimaud, Laurence ^{[1
]}

Jutand, Anny ^{[1
]}

Meignie, Alice ^{[1
]}

Romanov, Georgy ^{[1
]}

机构：

[1] Univ Paris 06, Sorbonne Univ, Dept Chim, Ecole Normale Super,PSL Res Univ,CNRS,UMR PASTEUR, F-75231 Paris, France

[2] ENSTA ParisTech, CNRS, ENSTA, Ecole Polytech,UMR 7652, F-91120 Palaiseau, France

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2014年 / 2014卷 / 22期

关键词：

Reaction mechanisms; Water chemistry; Reduction; Palladium; Amines; Phosphanes; ZEROVALENT PALLADIUM; COMPLEXES; PD(OAC)(2); REACTIVITY; MIXTURES; RATES; PD(0); HECK;

D O I：

10.1002/ejoc.201402519

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Tertiary amines such as EtN(iPr)(2) do not reduce [PdCl2(PPh3)(2)] into a Pd-0 complex. The latter is formed only after the addition of water (generation of HO-), as was reported by Grushin and Alper for NEt3. The mechanism of the Pd-II/Pd-0 reduction performed in the presence of an excess amount of PPh3 is established quantitatively by means of electrochemical techniques that provide kinetic data (determination of the equilibrium and rate constants) for the disappearance of [PdCl2(PPh3)(2)] and the formation of [Pd-0(PPh3)(3)]. [PdCl(OH)(PPh3)(2)] is formed, which allows reductive elimination between OH and the ligated PPh3 (zero-order reaction for PPh3), and this leads to a Pd-0 complex. The reducing agent is ligated PPh3, which ultimately yields (O)PPh3. The rate of the overall reduction process is controlled by the amount of water that imposes the concentration of HO-.

引用

页码：4709 / 4713

页数：5

共 19 条

[1]

Amatore C, 1996, NEW J CHEM, V20, P1143

[2] Formation of anionic palladium(0) complexes ligated by the trifluoroacetate ion and their reactivity in oxidative addition [J].