CHARGE TRANSFER INDUCED LIGAND SUBSTITUTION REACTIONS: THE REDUCTION ELECTROCHEMISTRY OF W(CO)//4 L//2 (L//2 equals aromatic diimine).

Complexes of the form W(CO)//4L//2 (L//2 equals aromatic diimine) can be described within the framework of a one electron picture. Thus, electrochemical reduction of a species such as W(CO)//4 bpy (bpy equals bipyridine) is expected to yield a stable, but highly reducing, left bracket W(CO)//4bpy right bracket ** minus species in which the added electron resides in the bipyridal ligand. In fact, cyclic voltammetric studies indicate an EC process at scan rates below 200mv, and bulk reduction of left bracket W(CO)//4bpy right bracket leads to the electrocatalytic loss of exactly one CO ligand per complex. If this process is carried out in the presence of an alternate ligand a high yield synthesis of the substituted complex is obtained.