Reaction of μ-oxobis(phthalocyaninatoiron(III)) in pyridine/water. Evidence for a slow reacting oxophthalocyaninatoiron(IV) compound

Unequivocal evidence about the presence of Fe(III) in μ-oxo-bis[tetrakis(t-butyl)phthalocyaninatoiron]

“…The inset is an enlargement of a single step (third step) and shows the graphical method followed to evaluate the contribution of LAA and DHA to the reduction of complex 3. with pyridine to yield the bispyridine adduct 3. The spectrum of the latter is very close to that shown by the ring unsubstituted m-oxo complex dissolved in pyridine [16]. (2).…”

“…Although it was earlier reported that the m-oxo compound dissolved in a coordinating solvent, such as py, was unstable and yielded almost quantitatively the Fe(II) bis adduct PcFe(py) 2 [5,7,15], a more complete study of this aspect was published recently [16]. It has been demonstrated that the reaction occurs in two consecutive steps.…”

The reaction of μ-oxo-bis(phthalocyaninato)iron(III) with hydrogen sulphide in the presence of pyridine: Evidence for axial coordination of dichloromethane

“…This behavior is reminiscent of what is observed when 4 is allowed to react in pure pyridine containing small amounts of water [14]. In this case quantitative conversion of 4 to a reduced monomeric Fe(II) species is achieved through an autocatalytic step, believed to be a disproportionation reaction, followed by a slow first order step where the metal-oxidized form, possibly (py)[(FePc)O], undergoes reduction.…”

“…The monomeric species 3 was identified on the basis of the spectrum at the end of the reaction, which was coincident with that of an authentic sample of 3. The mole ratio to the dimeric species 4 was determined on the basis of the molar extinction coefficients reported in the literature [11][12][13][14] and found to be 3:4 = 2.00 ± 0.05.…”

Reengineering of Organic-Based Metal Active Sites for Oxidations and Oxygenations

“…Halogenation induces destabilizing ring-distortions, but accelerates the catalyzed autoxidation rate-determining step. Interestingly free (48) and encapsulated FePc (45), form catalytically active PcFe(IV)=0. Electronic deficiency does not necessarily preclude the formation of Fe=0: nonperipherally substituted Fe(CF 3 ) 8 Pc forms with TBHP a ferryl group that oxygenates via oxo group transfer phosphines (49), but not alkanes.…”