Journal of Physical Chemistry A, Vol.102, No.29, 5749-5753, 1998
Reduction of Ru(bpy)(2)(AB)(2+) (bpy = 2,2 '-bipyridine, AB = 2,2 ' : 3 ',2 '' : 6 '',2 '''-quaterpyridine) in aqueous solution. A pulse radiolysis study
The one-electron reduction of Ru(bpy)(2)(AB)(2+), hereafter RuAB(2+), where bpy = 2,2'-bipyridine and AB = 2,2':3',2 ":6 ",2'"-quaterpyridine, in aqueous solution has been studied using pulse radiolysis. RuAB(2+) is reduced by e(aq)(-) (k = 6.2 x 10(10) M-1 s(-1) at ambient ionic strength (I) and k = 4.6 x 10(10) M-1 s(-1) at I = 0.1 M) and by CO2.- radical (k = 1 x 10(8) M-1 s(-1) at I = 0.1 M), generating RuAB(.+). The spectra of RuAB(.+) and its conjugated acid (RuABH(. 2+)) were obtained; the pK(a) of RuABH(. 2+) (8.0) has been determined. The rate constants for the protonation of RuAB(.+) (k(H) = 7.9 x 10(9) M-1 s(-1)) and the deprotonation of RuABH(. 2+) (k(-H) = 79 s(-1)) have been evaluated as have the rate constants for proton exchange (k(f) = 3.4 x 10(7) M-1 s(-1) and k(r) = 5.5 x 10(6) M-1 s(-1)) between the RuAB(.+)/RuABH(. 2+) and H2PO4-/HPO42- couples. The results from this work are compared with those obtained previously for 13 Ru(II) complexes that contain bpy, bpm (2,2'-bipyrimidine), bpz (2,2'-bipyrazine), and pypm (2-(2'-pyridyl)pyrimidine) ligands. In addition, since RuAB(2+) can be viewed as a substituted Ru(bpy)(3)(2+) complex that contains a bpy residue, a comparison is also made of the reductions of RuAB(2+) and bpy.
Keywords:ONE-ELECTRON REDUCTION;GENERATED RADICALS;HYDROXYL RADICALS;HYDROGEN-ATOMS;COMPLEXES;ION;1;10-PHENANTHROLINE;QUATERPYRIDINE;POTENTIALS;REACTIVITY