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Intermediates formed by laser flash photolysis of [PtCl(6)](2-) in aqueous solutions.
Authors:Irene V Znakovskaya  Yulia A Sosedova  Evgeni M Glebov  Vjacheslav P Grivin  Victor F Plyusnin
Institution:Department of Natural Sciences, Novosibirsk State University, 630090 Novosibirsk, Russian Federation.
Abstract:The stationary photolysis of PtCl(6)](2-) in aqueous solutions (10(-5)-10(-4) M) at the region of 313 nm leads to its photoaquation with a quantum yield of 0.19. Laser flash photolysis experiments (308 nm) provided evidence of the formation of Pt(iii) intermediates, namely PtCl(4)(OH)(H(2)O)](2-) and PtCl(4)](-), and Cl(2) (-) radical anions. The Pt(iii) complexes formed as a result of an intrasphere electron transfer from Cl(-) ligands to the excited Pt(iv) ion. However, the main ( approximately 90%) photolysis channel was not accompanied by the transfer of Cl atoms to the solvent bulk. The photoaquation of PtCl(6)](2-) results from the back electron transfer in the secondary geminate pair, PtCl(5)(H(2)O)](2-)-Cl. The relative yield of Pt(iii) intermediates, recorded after the completion of all processes in the geminate pair, was less than 10% of the number of disappearing initial PtCl(6)](2-) complexes.
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