The photochem. prepn. of the oxochloro complexes, UOCl3, UOCl5(C5H5NH)2, and U(OEt)5, is described. The absorption spectra of these U(V) complexes were measured and discussed. Irradn. of [UO2Cl2•(C5H5N)2] in dry EtOH and in the presence of radical scavengers is considered to yield UO2Cl as primary photoproduct which gives rise by thermal or secondary photochem. reaction to UOCl3. Thermal reaction of UOCl3 with pyridinium hydrochloride, formed in the photoreaction mixt., leads to UOCl5(C5H5NH)2 formation. Subsequent photoreaction of UOCl5(C5H5NH)2 produces U(OEt)5. A photochem. pathway to U(V) complexes compatible with the exptl. observations is proposed.
Photochemistry of Actinide Complexes. III. The Photoproduction Mechanism of Uranium(V) Oxochloro-Complexes.
DI BERNARDO, PLINIO;
1976
Abstract
The photochem. prepn. of the oxochloro complexes, UOCl3, UOCl5(C5H5NH)2, and U(OEt)5, is described. The absorption spectra of these U(V) complexes were measured and discussed. Irradn. of [UO2Cl2•(C5H5N)2] in dry EtOH and in the presence of radical scavengers is considered to yield UO2Cl as primary photoproduct which gives rise by thermal or secondary photochem. reaction to UOCl3. Thermal reaction of UOCl3 with pyridinium hydrochloride, formed in the photoreaction mixt., leads to UOCl5(C5H5NH)2 formation. Subsequent photoreaction of UOCl5(C5H5NH)2 produces U(OEt)5. A photochem. pathway to U(V) complexes compatible with the exptl. observations is proposed.Pubblicazioni consigliate
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