期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 11, 期 5, 页码 1565-1573出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200400811
关键词
C-C coupling; carbenes; insertion; palladium; transmetalation
Transmetalation of an aminocarbene moiety from [W(CO)(5){C(NEt2)R}] to palladium leads to isolable monoaminocarbene palladium aryl complexes [(Pd(mu Br)Pf[C(NEt2)R])(2)] (R=Me, Ph; Pf=C6F5). When [W(CO)(5){C(OMe)R}] is used, the corresponding palladium carbenes cannot be isolated since these putative, more electrophilic carbenes undergo a fast migratory insertion process to give alkyl palladium complexes. These complexes could be stabilized in the eta(3)-allylic form for R=2-phenylethenyl or in the less stable eta(3)-benzylic fashion for R=Ph. Hydrolysis products and a pentafluorophenylvinylic methyl ether (when R=Me) were also observed. The monoaminocarbenes slowly decompose through carbene-aryl coupling to produce the corresponding iminium salts and, depending on the reaction conditions, the corresponding hydrolysis products. The electrophilicity of the carbene carbon, which is mainly determined by the nature of the heteroatom group, controls the ease of evolution by carbenearyl coupling. Accordingly, no carbene-aryl coupling was observed for a diaminocarbene palladium aryl complex.
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