Benzo substitution cis to the nitrogen of 2,2'-bipyridyl (bipy), to form 2-(2'-pyridyl)quinoline
(pq), transforms the tris-complex with iron(11) from
low spin in Fe(bipy)32+ to
essentially high spin but near the crossover in Fe(pq)32+.
For this complex, the ligand field splitting near the crossover, Δc is estimated from magnetic and spectral
data as c. 12000 cm-l. A similar value but 150 cm-l lower
is estimated for the analogous complex with the sterically related ligand
2-methyl-1,10-phenanthroline. This apparent difference in Δ values could
arise from a direct change in ligand field potential, or from other factors,
such as a change in distortion effects. Due to steric hindrance, pq prefers to form bis-complexes Fe(pq)2X2,
pseudooctahedral and high spin, with suitable monodentates, X = Cl2 Br, NCS, ClO4. Double benzo substitution of bipy to form 2,2'-biquinolyl (biq)
so increases steric hindrance that the tris-complex could not be formed.
Instead biq forms pseudotetrahedral
complexes Fe(biq)22+ and Fe(biq)X2 (X = Cl, Br).
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