Facile Ar-CF3 bond formation at Pd.: Strikingly different outcomes of reductive elimination from [(Ph3P)2Pd(CF3)Ph] and [(Xantphos)Pd(CF3)Ph]

被引:274
作者
Grushin, Vladimir V. [1 ]
Marshall, William J. [1 ]
机构
[1] DuPont Co Inc, Cent Res & Dev, Expt Stn, Wilmington, DE 19880 USA
关键词
D O I
10.1021/ja064935c
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Facile and highly selective perfluoroalkyl-aryl reductive elimination from a metal center (Pd) has been demonstrated for the first time. At temperatures as low as 50-80 °C, [(Xantphos)Pd(Ph)CF3] undergoes remarkably clean decomposition to produce CF3Ph in high yield and selectivity. In contrast, analogous trifluoromethylpalladium aryls stabilized by rigid cis-chelating ligands such as dppe are completely unreactive at temperatures up to 130-140 °C. Decomposition of [(Ph3P)2Pd(Ph)CF3] in the presence of PhI in benzene at 60 °C does not produce PhCF3 but rather leads to [(Ph3P)2Pd(Ph)I] and [Ph4P]+[(Ph3P)Pd(CF3)3]- in a 2:1 ratio with high selectivity. Copyright © 2006 American Chemical Society.
引用
收藏
页码:12644 / 12645
页数:2
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