Electron Transfer Reactions of Peroxydisulfate and Fluoroxysulfate Reactions with the Cyanide Complexes M(CN)<i><sub>n</sub></i><sup>4-</sup> (MFe(II), Ru(II), Os(II), Mo(IV), and W(IV))
作者:Ulrik Kläning、Jørgen R. Byberg、Kim Daasbjerg、Knud Sehested、Evan H. Appelman
DOI:10.1021/jp0654157
日期:2007.3.1
stoichiometry and the kinetics of oxidation of the cyanide complexes M(CN)n4- (M = Fe(II), Ru(II), Os(II), Mo(IV), and W(IV)) by the peroxydisulfate ion, S2O8(2-), and by the much more strongly oxidizing fluoroxysulfate ion, SO4F-, were studied in aqueous solutions containing Li+. Reactions of S2O8(2-) with M(CN)n4- are known to be strongly catalyzed by Li+ and other alkali metal ions, and this applies
过氧二硫酸根离子对氰化物配合物M(CN)n4-(M = Fe(II),Ru(II),Os(II),Mo(IV)和W(IV))的化学计量和氧化动力学在含Li +的水溶液中研究了S2O8(2-)和更强氧化性的氟代硫酸根离子SO4F-。已知S2O8(2-)与M(CN)n4-的反应被Li +和其他碱金属离子强烈催化,这也适用于SO4F-的相应反应。已经发现S 2 O 8(2-)和SO 4 F-的主要反应都是单电子过程,其中相同强的OO和OF键断裂。S2O8(2-)的一级反应包括一步生成M(CN)n3-,SO4-和SO42-,而SO4F-的一级反应包括两个平行的单电子步骤,一个步骤导致M(CN) )n3-,SO4-和F-,另一个产生M(CN)n-1(2-),CN-,SO4-和F-。Li +催化的SO4F-和S2O8(2-)与M(CN)n(4-)的反应以及S2O8(2-)的未催化反应的速率常数与标准反