IONIC-STRENGTH EFFECTS ON ELECTRON-TRANSFER IN THE INVERTED REGION

被引:28
作者
CHEN, PY [1 ]
MECKLENBURG, SL [1 ]
DUESING, R [1 ]
MEYER, TJ [1 ]
机构
[1] UNIV N CAROLINA, DEPT CHEM, CHAPEL HILL, NC 27599 USA
关键词
D O I
10.1021/j100128a011
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Rate constants (k) for the intramolecular electron transfer reaction fac-[Re(I)(bpy.-)(CO)3(py-PTZ.+)](PF6) --> fac-[Re(I)(bpy)(CO)3(py-PTZ)](PF6), which occurs in the inverted region, were measured at 295 K in 1,2-dichloroethane solutions at different ionic strengths with [N(n-C4H9)4](PF6) as the added electrolyte (bpy is 2,2'-bipyridine, py-PTZ is 10-(4-picolyl)phenothiazine). The rate constant for electron transfer varies with ionic strength from 1.05 X 10(7) s-1 (mu = 0.0002 m) to 1.65 x 10(7) s-1 (mu = 0.32 m). The variation of k with ionic strength is consistent with an energy gap law dependence for the electron transfer reaction. Based on conductivity measurements at a series of concentrations, the related salt fac-[Re(I)(bpy)(CO)3(4-Etpy)](PF6) (4-Etpy is 4-ethylpyridine) is nearly completely ion-paired in 1,2-dichloroethane even in the absence of added supporting electrolyte.
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页码:6811 / 6815
页数:5
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