Journal of Physical Chemistry p. 3436 - 3439 (1982)
Update date:2022-08-16
Topics:
Foreman, T. K.
Bonilha, J. B. S.
Whitten, D. G.
Irradiation of Ru(bpy)32+ in the presence of Ag+ in acetonitrile leads to the photosubstitution product Ru(bpy)2(CH3CN)22+.The reaction does not occur in the absence of Ag+ or acetonitrile; although Ag+ quenches the luminescent MLCT state of Ru(bpy)32+, a kinetic analysis indicates the photosubstitution does not originate from this excited state.The most reasonable mechanism for the process involves decay of the MLCT state via a d-d excited state to a ligand-labilized intermediate which is interpreted by Ag+ in a process which assists the substitution by removal of a bpy ligand.This mechanism is thus parallel to anion-induced substitution reactions which evidently proceed via competitive anion-ligand capture of the same or similar intermediates.
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