Rates of the oxidative addition of benzyl halides to a metallacyclic palladium(II) complex and of the reductive elimination from a benzyl-palladium(IV) complex

被引：47

作者：

Amatore, Christian ^{[1
]}

Catellani, Marta ^{[2
]}

Deledda, Sara ^{[1
]}

Jutand, Anny ^{[1
]}

Motti, Elena ^{[2
]}

机构：

[1] UPMC, Ecole Normale Super, CNRS,UMR 8640, ENS,Dept Chim, F-75231 Paris 5, France

[2] Univ Parma, Dipartimento Chim Organ & Ind, I-43100 Parma, Italy

来源：

ORGANOMETALLICS | 2008年 / 27卷 / 18期

关键词：

D O I：

10.1021/om800015x

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Pd(II) metallacyclic complexes are key intermediates in sequential reactions in which three new C-C bonds are formed in an aromatic ring. The Pd(II) metallacyclic complex 10 with phenanthroline as ligand undergoes oxidative addition to benzyl bromide or chloride in DMF to generate benzyl-Pd(IV) complexes. The rate constant of the oxidative addition is determined by means of electrochemical techniques, with the expected reactivity order PhCH2Br (k(1Br) = 3.6 M-1 s(-1)) > PhCH2Cl (k(1Cl) = 6 x 10(-3) M-1 s(-1)) at 29 degrees C. When the benzyl-Pd(IV) complex is generated from PhCH2Br, the oxidative addition is followed by a slow C-C reductive elimination, which gives a Pd(II) complex. The rate constant of the reductive elimination has been determined in DMF (k(2Br) = 6 x 10(-4) s(-1)) at 29 degrees C.

引用

页码：4549 / 4554

页数：6

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