Chain processes in the photochemistry of PtIV halide complexes in aqueous solutions
作者:E. M. Glebov、A. V. Kolomeets、I. P. Pozdnyakov、V. P. Grivin、V. F. Plyusnin、N. V. Tkachenko、H. Lemmetyinen
DOI:10.1007/s11172-013-0221-z
日期:2013.7
The mechanisms of the photoaquation of PtCl62− and PtBr62− complexes were compared by the experimental results on stationary photolysis, nanosecond laser flash photolysis, and ultrafast pump-probe spectroscopy. The formation of the photoaquation product of the bromide complex, viz., PtBr5(H2O)−, was shown to proceed via the mechanism of heterolytic cleavage of the Pt-Br bond, and the platinum cation
通过固定光解、纳秒激光闪光光解和超快泵浦探针光谱的实验结果比较了 PtCl62- 和 PtBr62- 配合物的光水合机理。溴化物配合物的光水合产物 PtBr5(H2O)- 的形成是通过 Pt-Br 键的异裂机制进行的,铂阳离子在整个过程中保持四价. 对于氯化物络合物,发现 Pt-Cl 键裂解是均裂的,光水合产物的前体,即 PtCl5(H2O)-络合物,是三价铂依次相互转化的中间体。这些中间体的反应决定了光水化过程的链特征。