Facile Ar−CF3 Bond Formation at Pd. Strikingly Different Outcomes of Reductive Elimination from [(Ph3P)2Pd(CF3)Ph] and [(Xantphos)Pd(CF3)Ph]

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, ana...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2006-10, Vol.128 (39), p.12644-12645
Main Authors: Grushin, Vladimir V, Marshall, William J
Format: Article
Language:English
Subjects:
Chemistry
Crystallography, X-Ray
Exact sciences and technology
General and physical chemistry
Hydrocarbons, Fluorinated - chemical synthesis
Hydrocarbons, Fluorinated - chemistry
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Palladium - chemistry
Phosphines - chemical synthesis
Phosphines - chemistry
Xanthenes - chemistry
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Summary: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.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja064935c