Intermolecular chelate linkage isomerism of the hydroxyimino group in the nickel(II), copper(II), and palladium(II) complexes of quadridentate Schiff-base ligands.
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概要
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The C-nitrosation of bivalent quadridentate β-imino ketone complexes of nickel(II), copper(II), and palladium(II), with nitrosating reagents has been investigated. The chemical analysis and spectroscopic results reveal that one of the α-CH groups of the coordinated lignad undergoes selective nitrosation forming mono(hydroxyimino) derivative. The hydroxyimino group introduced coordinates through either N- or O- atom to metal(II) by dislodging the carbonyl group already coordinated. This gives rise to two linkage isomers, one with N-bonded and the other with O-bonded hydroxyimino group in the case of nickel(II) (except for <B>1d</B>) and palladium(II), and a single isomer with O-bonded hydroxyimino group in copper(II) complexes. The isomers obtained from <B>1b</B> and <B>1i</B> have been separated by column chromatography. In chloroform each of the isomers of nickel(II) isomerizes to give an equilibrium mixture of two isomers, but not those of copper(II) and palladium(II).
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著者
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Dixit N.
Department of Inorganic and Physical Chemistry, Indian Institute of Science
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Sudha B.
Department of Inorganic and Physical Chemistry, Indian Institute of Science
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Patel C.
Department of Inorganic and Physical Chemistry, Indian Institute of Science