Intermediates formed by laser flash photolysis of [PtCl(6)](2-) in aqueous solutions. |
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Authors: | Irene V Znakovskaya Yulia A Sosedova Evgeni M Glebov Vjacheslav P Grivin Victor F Plyusnin |
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Institution: | Department of Natural Sciences, Novosibirsk State University, 630090 Novosibirsk, Russian Federation. |
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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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