Photolytic and radiolytic study of platinum(III) complex ions containing aquo and chloro ligands

Primary reactions in the photochemistry of hexahalide complexes of platinum group metals: A minireview

“…The same primary reactions were assumed in acetonitrile [62] and chloroform [63,64]. Nevertheless, the overall photochemical process is photoaquation, yielding the Pt IV Cl 5 (H 2 O) À complex in the first stage [6,8,9,11,12,65,66]. Provided that atomic chlorine is produced in the primary Reaction (8), photoaquation may proceed via a chain reaction.…”

“…Provided that atomic chlorine is produced in the primary Reaction (8), photoaquation may proceed via a chain reaction. Both the experimental data [6,8,9,11,12,65,66] and the quantum chemical calculations [66][67][68] show that Pt III Cl 4Àn X n (n = 1-3; X = OH À , H 2 O) is the most probable chain carrier [6,11]. Depending on the experimental parameters (irradiation wavelength, light intensity, initial concentration of the complex, pH), the quantum yield may be either below unity [6,9,11] or significantly higher than unity [11,12].…”

“…The principal focus has been on the Pt IV Cl 6 2À complex. The main points investigated were the reaction intermediates [6][7][8][9][10][11][12], unusual aquation chain reactions [11,12] and the dramatic differences in the properties of the isoelectronic Pt IV Cl 6 2À and Pt IV Br 6 2À complexes [2,3].…”

Primary photochemical processes for PtCl62− complex in acetonitrile solutions

“…In aqueous solutions, the integral photochemical process is photoaquation with the formation of the Pt IV Cl 5 (H 2 O) À complex as primary photoproduct [20][21][22][23][24][25][26][27]. Mechanism of photoaquation includes redox stages.…”

Chain Mechanism of Radical-Initiated Ligand Exchange in PtCl42- in Aqueous Solution

“…Short-lived Pt(III) complexes containing aquo and chloro ligands have indeed been found in a pulse radiolysis study, and their role as intermediates in ligand exchange has been pointed out. 2 We wish to report on the observation of an extremely fast Cl -f H 2 O ligand exchange in PtCl 4 2-, which is initiated by certain organic radicals. A chain mechanism is also postulated, although there can be only speculation at the present time about the nature of the chain carrier.…”