HORVATH, O and VOGLER, A (1993) PHOTOREDOX CHEMISTRY OF CHLOROMERCURATE(II) COMPLEXES IN ACETONITRILE. INORGANIC CHEMISTRY, 32 (24). pp. 5485-5489. ISSN 0020-1669,
Full text not available from this repository.Abstract
The kinetically labile chloromercurates(II) have rather high stepwise formation constants in acetonitrile; even for HgCl42- a value of 1.07 X 10(4) M-1 was determined. The ultraviolet spectra of these complexes are characterized by ligand-to-metal charge-transfer transitions of different energies and intensities. Their photolysis leads to the formation of Hg(I) and Cl. in the primary photochemical reaction. The mercury(I) monomers recombine to give Hg2Cl2, while chlorine radicals are reconverted to Cl-, increasing the Cl-/Hg(II) ratio in the solution. In considerable excess of Cl- ([CI-] = 5 X 10(-3) M at 4.5 X 10(-5) M HgCl42-) mercury(I) species undergo disproportionation giving Hg0 as end product. The higher the ligand number of the complex, the lower is the quantum yield for the overall reaction: 5.3 10(-2), 1.35 X 10(-2), and 9.5 X 10(-3) for HgCl2, HgCl3-, and HgCl42-, respectively, in deaerated solution at lambda(ir) = 254 nm. In the presence of air quantum yields are lower and the main product is Hg2Cl2 in all cases. Ethanol enhances the efficiency of the photoreduction but only in argon-saturated systems, indicating competitive reactions of the Hg(I) monomers formed in the primary step and a considerable oxygen sensitivity of Hg0 as well.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CHLOROCOPPER(II) COMPLEXES; QUANTUM YIELDS; MERCURY(II); |
| Depositing User: | Dr. Gernot Deinzer |
| Last Modified: | 19 Oct 2022 08:42 |
| URI: | https://pred.uni-regensburg.de/id/eprint/53665 |
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