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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)

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