Nuclear magnetic resonance studies of copper(I) complexes of imidazoles. I Their preparation, characterization, equilibria, and reaction with carbon monoxide.
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概要
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Various copper(I) complexes with monodentate imidazole(im) have been prepared from [Cu(CH<SUB>3</SUB>CN)<SUB>4</SUB>]X (X=ClO<SUB>4</SUB><SUP>−</SUP> and PF<SUB>6</SUB><SUP>−</SUP>) in acetone. Their characterization has principally been made by <SUP>1</SUP>H NMR spectroscopy. Binary copper(I) complexes are [Cu(im)<SUB>2</SUB>]<SUP>+</SUP> (<B>2</B>) and [Cu(im)<SUB>3</SUB>]<SUP>+</SUP> (<B>3</B>), while the monoimidazole complex is a ternary two- or four-coordinate complex (<B>1</B>). In contrast with <B>2</B> and <B>3</B>, quantitative formation of [Cu(im)<SUB>4</SUB>]<SUP>+</SUP> (<B>4</B>) does not occur in acetone. Even at [im]/[Cu]<2, <B>2</B> forms more preferentially than <B>1</B>. This is due to the linear structure of <B>2</B>. <B>2</B> and <B>3</B> provide stable CO adducts, both of which display complete reversibility. The affinity for CO of <B>3</B> is much stronger than that of <B>2</B>. Pyrazole copper(I) complexes were also prepared and examined as a comparison with imidazole complexes. Monodentate pyrazole hardly gives two- and three-coordinate complexes. This is attributable to its low basicity in contrast with that of imidazole.
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