期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 134, 期 1, 页码 606-612出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja209424z
关键词
-
资金
- Swiss National Science Foundation
- ETH Zurich
The catalysis derived from the dinuclear Pd(I)-Pd(I) complex, {[PtBu3]-PdBr}(2), has been studied with experimental, computational, and spectroscopic techniques. Experimental selectivity studies were performed, and the reactivity was subsequently investigated with density functional theory (B3LYP-D and M06L) to deduce information on the likely active catalytic species. The reactivity with aryl chlorides and bromides was found to be inconsistent with direct catalytic involvement of the Pd(I) dimer but consistent with mononuclear Pd(0) catalysis. Computational studies suggest that precatalyst transformation to the active catalytic species does not proceed via a direct disproportionation mechanism; a reductive pathway is the most likely scenario instead. Through P-31 NMR investigations it was identified that the combination of ArB(OH)(2), KF, and water triggers the conversion of the precatalyst to Pd(PtBu3)(2) and, most likely, Pd-black as a competing side process, explaining the incomplete conversions of aryl chlorides in Suzuki cross-coupling reactions under Pd(I) dimer conditions. New applications in highly regio- and chemoselective transformations in short reaction times at room temperature are also demonstrated.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据