Spectroscopic studies of copper(I) complexes of 1,8-di(2-pyridyl)-3,6-dithiaoctane in a nonaqueous solvent. The halide-ion effect on their structure.
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概要
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The complexes of 1,8-di(2-pyridyl)-3,6-dithiaoctane(pdto) with CuX(X=Cl and Br) and [Cu(CH<SUB>3</SUB>CN)<SUB>4</SUB>]ClO<SUB>4</SUB> have been synthesized in chloroform, methanol, ethanol, and acetone. Their absorption spectra show an intense metal-to-ligand charge-transfer band at 307 nm: This band is assigned to pyridyl nitrogen←Cu. [Cu(pdto)]<SUP>+</SUP> (<B>1</B>) has been prepared from [Cu(CH<SUB>3</SUB>CN)<SUB>4</SUB>]ClO<SUB>4</SUB>, its pdto acting as a four-coordinate ligand. CuX reacts with pdto to yield two complexes: One is <B>1</B>, and the other is [CuX(pdto)] (<B>2</B>). Both complexes are four-coordinate, but in the <B>2</B> one of the two pyridyl groups is dissociated. The complex <B>2</B> is unstable and is oxidized by oxygen. Neither complex reacts with CO, indicating the tight binding of pdto with Cu(I). The <B>1</B> and <B>2</B> are equilibrated in solution. The <SUP>1</SUP>H NMR spectra well demonstrate that <B>2</B> is dominant in chloroform and that <B>1</B> is the principal form in alcohol, while the <B>1/2</B> ratio is 3/7. This solvent-dependence is ascribed to the coordination ability and/or polarity of the solvent.
- 公益社団法人 日本化学会の論文
著者
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Munakata Megumu
Department Of Chemistry Faculty Of Science And Technology Kinki University
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Kitagawa Susumu
Department Of Chemistry Faculty Of Science Tokyo Metropolitan University
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Okada Shoji
Department of Chemistry, Faculty of Science and Technology, Kinki University
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