Catalyzed substitutions on cationic palladium(II) complexes. III. Mercury(II) catalyzed displacement of coordinated thiocyanate and selenocyanate linkage isomers

• Published in: Inorganica Chimica Acta Vol. 30; pp. 29 - 34
• Main Authors: Cusumano, M., Guglielmo, G., Marricchi, P., Ricevuto, V.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 1978
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/S0020-1693(00)89011-8

A kinetic study of Hg 2+ catalyzed solvolysis of linkage isomers [Pd(AAA)XCN/NCX] + (AAA = 1,1,7,7-tetraethyldiethylenetriamine (Et 4dien) and 4-methyl-1,1,7,7-tetraethydiethylenetriamine (MeEt 4dien); X = S, Se) has been carried out in methanol at 25 °C. The kinetic results show that the catalytic efficiency of mercury(II) in removing the thiocyanate or selenocyanate ligands is greater in the PdXCN substrates than in the PdNCX ones, depending on whether the sulfur or selenium atom on which the attack by Hg 2+ takes place, is bonded directly to palladium(II). The kinetic data for the isomerization and substitution reactions are also reported.