ja044090+_si_001.pdf (175.27 kB)
The Remarkable Axial Lability of Iron(III) Corrole Complexes
journal contribution
posted on 2005-05-11, 00:00 authored by Crisjoe A. Joseph, Peter C. FordFlash photolysis of nitrosyl tris(aryl)corrolate complexes of iron(III), Fe(Ar3C)(NO) (Ar3C3- =
5,10,15-tris(4-nitro-phenyl)corrolate (TNPC3-), 5,10,15-tris(phenyl)corrolate (TPC3-) or 5,10,15-tris(4-tolyl)corrolate (H3TTC3-)) leads to NO labilization. This is followed by the rapid reaction of NO with FeIII(C) to
regenerate the starting complex. The second-order rate constants for the back reactions (kNO) were
determined to be many orders of magnitude faster than the corresponding reactions of ferric porphyrin
complexes and indeed are reminiscent of the very large values seen for those of the corresponding ferrous
porphyrin analogues. These data are interpreted in terms of the strongly electron-donating character of
the trianionic corrolate ligand and the likely triplet electronic configuration of the iron(III) complex. These
reduce the affinity of the metal centers to Lewis bases to the extent that axial ligands bind very weakly or
not at all. This property is illustrated by the nearly identical kNO values (∼109 M-1 s-1 at 295 K) recorded
for the back reaction of FeIII(TNPC) with NO after flash photolysis of Fe(TNPC)(NO) in toluene solution
and in THF solution. Softer Lewis bases have a somewhat greater effect; for example, studies in 1:9 (v:v)
acetonitrile:toluene and 1:9 pyridine:toluene gave kNOvalues decreased ∼33% and ∼85%, respectively,
but these both remain >108 M-1 s-1. The potential roles of Lewis bases in controlling the dynamics of NO
addition to Fe(TNPC) in toluene was investigated in greater detail by determining the rates as a function
of pyridine concentration over a wide range (10-4 to 2.5 M). These data suggest that, while a monopyridine
complex, presumably Fe(TNPC)(py), is readily formed (K ≈ 104 M), this species is about one-sixth as
reactive as Fe(TNPC) itself. It appears that a much less reactive bis(pyridine) complex also is formed at
high [py] but the equilibrium constant is quite small (<1 M-1).