Intermediates formed by laser flash photolysis of [PtCl(6)](2-) in aqueous solutions.
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.
Znakovskaya
Irene V
IV
Department of Natural Sciences, Novosibirsk State University, 630090 Novosibirsk, Russian Federation.
Sosedova
Yulia A
YA
Glebov
Evgeni M
EM
Grivin
Vjacheslav P
VP
Plyusnin
Victor F
VF
D002713:Chlorine / Q000737:chemistry*; D002945:Cisplatin / Q000031:analogs & derivatives* / Q000737:chemistry; D007700:Kinetics; D007834:Lasers; D010782:Photolysis; D010984:Platinum / Q000737:chemistry*; D017671:Platinum Compounds / Q000737:chemistry* / Q000378:metabolism; D012996:Solutions; D014867:Water / Q000737:chemistry
D017671:Platinum Compounds; D012996:Solutions; D014867:Water; D010984:Platinum; D002713:Chlorine; D002945:Cisplatin; C038762:disodium hexachloroplatinate