Equilibria in complexes of N-heterocyclic molecules. Part 13. The racemization and dissociation of some tris(1,10-phenanthroline) and tris(2,2′-bipyridyl) complexes of iron-(II) and -(III)

Abstract
The racemization and dissociation of [Fe(phen)3]3+, together wrth the racemization of [Fe(phen)3]2+ and [Fe(bipy)3]3+, have been followed kinetically in aqueous acid solutions containing HCl, H2SO4, or HNO3, up to 100% acid concentration. The rates of racemization and dissociation of [FeL3]3+[L = 1,10-phenanthroline(phen) or 2,2′-bipyridyl(bipy)] are zero in 100% H2SO4, and the racemization of [Fe(phen)3]2+ reaches a limiting rate in ca. 11.0 mol dm–3 HCl. The kinetics of dissociation of [Fe(bipy)3]3+ are quite different from other reported complexes and a maximum rate is attained at ca, 3.0 mol dm–3 H2SO4. On the basis of the observations and previously reported data, a new mechanism for racemization and dissociation is proposed.

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