Summary
The kinetics of the inner selfredox reaction of Cu(dtph)2 (dtph = dithiophosphinate) was studied by e.p.r. The reaction is second order in CuII(dtph)2 with effective rate constant 5.5 dm3 mol−1s−1 (at 300 K); the plot of log keff/(1/T) is not of Arrhenius type, suggesting that keff depends on the equilibrium constant for the formation of a precursor between two molecules of CuII(dtph)2. On the other hand, the differences in a0 and aav (a0<aav) extracted from e.p.r. spectra in solution and frozen solution or magnetically dilute samples suggest that CuII(dtph)2 is associated in solution, whereas in the other two forms it is a monomer. The observed instability of CuII(dtph)2 towards inner selfredox reaction is compared to that of other sulphur-containing CuII complexes and discussed in terms of the relatively low redox potential of the ligand.
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Yordanov, N.D., Alexiev, V., Malakova, C. et al. Studies on intermolecular interactions of metal chelate complexes. VI. On the selfredox reaction of copper(II) dithiophosphinates. Transition Met Chem 8, 210–212 (1983). https://doi.org/10.1007/BF00620691
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DOI: https://doi.org/10.1007/BF00620691