Vv. Strelets, REDOX ACTIVATION OF ORGANOMETALLICS - THE ELECTROCHEMICAL INITIATION OF THE ISOMERIZATION-REACTIONS OF ORGANOMETALLIC PI-COMPLEXES, Russian journal of electrochemistry, 32(1), 1996, pp. 2-10
Basic principles governing redox activation of the 18-electron complex
es of transition metals are considered. In essence, this process conve
rts the above complexes to 17-electron or 19-electron radical-ions via
the abstraction or addition of an electron, respectively. The latter
radical-ions exhibit significantly enhanced reactivity. The feasibilit
y of the electrochemical initiation of the isomerization reactions for
complexes with polydentate ligands, which occur concomitant with a ch
ange in the metal coordination site, is shown using sandwich and semis
andwich pi-complexes of transition metals. Particular emphasis is plac
ed on examining reactions of inter-ring haptotropic isomerization for
pi-complexes of metals with polycyclic aromatic ligands that are induc
ed by electron transfer. The isomerization involves migration of the m
etal from one ring to another along the plane of the nn-electron syste
m of the ligand.