Some studies in inorganic complexes. XX. Further reactions of 2-thioaminopyridine

Abstract

The following complexes of 2-thioamidopyridine (thiopic) were prepared and studied : [RhCl₂ thiopic₂]Cl,2H₂O; [RhCl₂ thiopic₂][RhCl₄ thiopic]; [RhCl, thiopic₂]ClO₄; [RhBr₂ thiopic₂]ClO₄; [RhI₂ thiopic₂]ClO₄,H₂O; [Rh thiopic₃][ClO₄]₃; [Ag thiopic]ClO₄; [AuCl₂ thiopic][AuCl₄]; [Au thiopic₂][AuI₂]; [RuCl₂ thiopic₂], C₂H₅OH; [Os thiopic₃]Br₃; [Cr thiopic₃]Br₃; [MnI₃ thiopic₂]; [In thiopic₃]Cl₃,H₂O. The following substances were also prepared and studied: [RhI₂ pic₂]I₂,H₂O; [RhCl, en,]Cl,H₂O; [Rh phenan₃]Br₃ (where pic is 2-aminomethylpyridine, en is ethylenediamine, and phenan is 1,10-phenanthroline). The conductances of all of the aforementioned substances in NN?-dimethylformamide agreed with their structures as metal chelates as indicated. Studies of absorption spectra in the visible region were also made, and infrared spectra showed that bonding had occurred through the sulphur atom of the -C(=S)NH, group in the case of rhodium(III), gold(I), gold(III), ruthenium(II), osmium(III), and silver(I) complexes, whereas with chromium(III), manganese(II), and indium(III) coordination was by the nitrogen atom. Measurements of magnetic susceptibility showed that the rhodium(III), gold(I), gold(III), ruthenium(II), and osmium(III) complexes were spin-paired, whereas those of chromium(III) and manganese(II) were spin free.