2,2'-Azobis(pyridine) (abpy) as a multiply reducible tetradentate ligand. EPR evidence for the configurational dependence of intramolecular electron transfer in the stereoisomeric tris-chelate ruthenium complexes Ru(abpy)n(bpy)3-nm (n = 2, 3; m = 2+ to 3-)
, , , , , , und .
Inorganic Chemistry 32 (15): 3362--3368 (1993)

Fac- and mer-Ru(abpy)32+ (abpy = 2,2'-azobis(pyridine) and 2 out of the 3 possible diastereoisomers of Ru(abpy)2(bpy)2+ were isolated via HPLC and identified by their 1H NMR spectra. Electrochem. potentials for several 1-electron redn. steps and UV/visible spectroelectrochem. features vary to a small but detectable degree for the resp. pairs of isomers. The absence of a room-temp. EPR signal for 1 of the 2 isolated isomers of RuII(abpy-)(abpy)(bpy).bul.+ demonstrates the structural requirements for intramol. electron transfer. A 99,101Ru EPR hyperfine coupling of $\sim$0.8 mT was established for the previously reported radical ion Ru(abpy)(bpy)2.bul.+. The free a-azimino chelate is in mononuclear complexes of abpy render these systems suitable for the construction of polynuclear compds. The exceptional p-acceptor capability of abpy is illustrated by the reversible acceptance of $\geq$8 electrons by (Ru(bpy)22(μ,η4-abpy)n. on SciFinder(R)
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