Koordinationschemie der Azole

Tris(azolyl)methylthiolates are obtained in excellent yields via a new synthetic route considering both economic aspects and ease of preparation. Starting from thiophosgene and the silylated azole the bis(azolyl)thioketone is generated and subjected to the addition of a potassium azole anion. An improved synthesis for bis(pyrazolyl)thioketone has enabled the isolation of the intermediate pyrazole-1-carbothioyl-chloride, S=C(Cl)pyrazole, in quantitative yields which in turn has afforded the first asymmetric bis(azole), S=C(pyrazole)(triazole). Tris(azolyl)methylthiolates represent highly reactive nucleophiles that are easily transformed into mono- and bitopic tris(azolyl)methylthio-derivatives. The crystal structures of these compounds and their potential as ligands in coordination chemistry with various transition metals has been studied thoroughly.