Studies on intermolecular interactions of metal chelate complexes. V. copper(ii) dithiophosphate complexes: an example of an inner self-redox reaction |
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| Authors: | Nicola D Yordanov Valentin Alexiev Josef Macicek Tadeusz Glowiak David R Russell |
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| Institution: | (1) Institute of Organic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria;(2) Insitute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia;(3) Institute of Chemistry, University of Wroclaw, Wroclaw, Poland;(4) Department of Chemistry, The University, Leicester, UK |
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| Abstract: | Summary Studies of copper dithiophosphate (dtp) complexes by various physical methods, in the solid and the molten state as well as in solution, are reported. In the solid state all the complexes of dithiophosphate (RO)2PS
2
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R = CnH2n+1 (n=1–4), Ph, orcyclo-C6H11] are diamagnetic but in the molten state and in solution they are paramagnetic. Interconversions were found to be reversible, and the effect was ascribed to an inner self-redox reaction. Only the bulkyo-tolyl derivative is paramagnetic in the solid and molten states and in solution. It is proposed that the self-redox reaction involves association between two molecules of CuII(dtp)2 during crystallization, followed by formation of CuI(dtp)]2, and (RO)2P(S)S-S(S)P(OR)2, and then CuI(dtp)]4. The molecular structures of complexes with R = isopropyl ando-tolyl confirm these inferences.Part IV of this series: N. D. Yordanov, V. Iliev, and D. Shopov,Inorg. Chim. Acta, 60, 21 (1982). |
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