ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Properties of chlorocopper(II) complexes with triphenylphosphine, -arsine, or -stibine type ligands in solution. II. Chlorination of triphenylphosphine, -arsine, or -stibine as a result of mutual ligand effects in redox processes in chlorocopper(II) complexes

D. Makáňová, G. Ondrejovič, D. Valigura, and J. Gažo

Lehrstuhl für Anorganische Chemie der Slowakischen Technischen Hochschuley 880 37 Bratislava

Abstract:  The reaction of copper(II) chloride with Ph₃E (E = P, As, Sb) in acetonitrile and acetone leads to the chlorination of Ph₃E to give Ph₃ECI₂. By hydrolysis of this compound hydrogen chloride is set free in an amount representing half of the chlorine bonded in CuCI₂. The formation of Pb₃PCI₂ has also been proved by its isolation after the reaction of CuCI₂ with Pb₃P in acetonitrile and benzene. Also the compound Pb₃SbCI₂  has been isolated and identified as a product of the reaction of CuCI₂ with Ph₃Sb in acetone and methanol. The chlorination effect of CuCI₂ onPb₃E is explained as a consequence of the mutual influence of ligands through the central atom in intermediate chlorocopper(II) complexes with Pb₃Е; owing to the influence of n acceptor ligands Pb₃E a homolytic splitting off of one of the bonds Cu(II) -L takes place (E = P, As; L = CI).

Full paper in Portable Document Format: 285a604.pdf (in German)

Chemical Papers 28 (5) 604–608 (1974)