Reactivity of chloro(phthalocyaninato)iron(<scp>III</scp>) in pyridine–water

Monacelli, Fabrizio

doi:10.1039/dt9910003373

Cited by 4 publications

(1 citation statement)

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“…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.…”

Section: Reaction Between 4 and Hydrogen Sulphide Products And Stoicmentioning

confidence: 99%

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

Monacelli

Viola

2005

J. Porphyrins Phthalocyanines

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The oxo-bridged complex (py)FePc-O-FePc(py) (py = pyridine, Pc = phthalocyaninato dianion) reacts in dichloromethane with hydrogen sulphide giving elementary sulphur and the reduced (py) 2 (FePc) complex in the stoichiometric ratio 1:1. Under excess py and H 2 S, the reaction is firstorder and the rate constant at a given py concentration is an increasing function of the reducing agent concentration, with asymptotic tendency to a limiting value. This latter depends on the pyridine concentration being higher the lower is the base concentration. When the reaction is carried out in pure pyridine, the rate constant is, instead, a strictly linear function of [H 2 S], with zero intercept. A reaction mechanism is proposed where the dichloromethane is directly involved in the axial coordination about the iron centers and H 2 S competes efficiently with both pyridine and solvent.

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Section: Reaction Between 4 and Hydrogen Sulphide Products And Stoicmentioning

confidence: 99%