Effect of solvent and remote ligand substituents on the photochemical behaviour of copper(II) dithiocarbamates and dithiophosphates

• Published in: Transition metal chemistry (Weinheim) Vol. 26; no. 4-5; p. 388
• Main Authors: Sarova, Ginka H, Jeliazkova, Bojana G
• Format: Journal Article
• Language: English
• Published: Dordrecht Springer Nature B.V 01.01.2001
• ISSN: 0340-4285; 1572-901X
• DOI: 10.1023/A:1011004527292

The photochemical properties of bis(dithiocarbamato)Cu^sup II^, Cu(R^sup 1^dtc)^sub 2^, and bis(dithiophosphato)Cu^sup II^, Cu(R^sub 2^^sup 2^dtp)^sub 2^, complexes with different remote ligand substituents (R^sup 1^ = piperidine, morpholine, pyrrolidine and 4-phenylpiperazine; R^sup 2^ = Me, Et and i-Pr) have been studied in chloromethanes (CCl^sub 4^, CHCl^sub 3^, CH^sub 2^Cl^sub 2^), chloromethanes/EtOH and PhMe. The monomeric species Cu^sup II^(R^sup 1^dtc)Cl and its chloride-bridged dimeric form Cu^sub 2^(R^sup 1^dtc)^sub 2^Cl^sub 2^ were subsequently obtained during Cu(R^sup 1^dtc)^sub 2^ photolysis in chloromethane/EtOH mixtures and the steady-state concentration of Cu^sub 2^(R^sup 1^dtc)^sub 2^Cl^sub 2^ was found to depend on the EtOH content in the mixed solvents as well as on the nature of R^sup 1^ and the oxidising ability of the chloromethane. The appearance of the mixed-ligand complex Cu^sup II^(R^sub 2^^sup 2^dtp)Cl has been observed as an intermediate photoproduct after longer u.v.-irradiation of Cu(R^sub 2^^sup 2^dtp)^sub 2^ in chloromethanes/EtOH.[PUBLICATION ABSTRACT]