S. Kitagawa, M. Munakata, S. Okada
Nov 1, 1982
Citations
0
Influential Citations
2
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
The complexes of 1,8-di(2-pyridyl)-3,6-dithiaoctane(pdto) with CuX(X=Cl and Br) and [Cu(CH3CN)4]ClO4 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)]+ (1) has been prepared from [Cu(CH3CN)4]ClO4, its pdto acting as a four-coordinate ligand. CuX reacts with pdto to yield two complexes: One is 1, and the other is [CuX(pdto)] (2). Both complexes are four-coordinate, but in the 2 one of the two pyridyl groups is dissociated. The complex 2 is unstable and is oxidized by oxygen. Neither complex reacts with CO, indicating the tight binding of pdto with Cu(I). The 1 and 2 are equilibrated in solution. The 1H NMR spectra well demonstrate that 2 is dominant in chloroform and that 1 is the principal form in alcohol, while the 1/2 ratio is 3/7. This solvent-dependence is ascribed to the coordination ability and/or polarity of the solvent.