Aromatic Metalation Reactions by Palladium(II) and Platinum(II) on Aromatic Aldoximes and Ketoximes
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概要
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<I>Ortho</I> metalation by palladium(II) was observed in the reaction of lithium tetrachloropalladate(II) with various aromatic aldoximes and ketoximes in methanol in the presence of sodium acetate. The obtained chloro-bridged complexes(<B>7</B>) possessed both <I>ortho</I>-attached palladiumcarbon σ-bonding and palladium-nitrogen coordinate bonding to oximes. Reactions of <I>O</I>-acyl and <I>O</I>-methyl oximes with lithium tetrachloropalladate(II) were also carried out. An <I>ortho</I> metalation was observed in the former case, but dichlorobis(<I>O</I>-methyl oxime)palladium(II) type complexes containing no palladium-carbon σ-bonds were predominantly formed in the latter case. The bridge-splitting reaction of chloro-bridged complexes with triphenylphosphine and the metathetic reaction with sodium bromide in acetone were carried out. In the case of potassium tetrachloroplatinate(II), an <I>ortho</I> metalation reaction was observed giving the complexes(<B>10</B>) but chloro-bridged complexes could not be isolated.
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