✦ LIBER ✦

Spectroscopic and kinetic studies of the reactions of iron(III) porphyrins with alkyl thiols

✍ Scribed by Bradford B. Wayland; James C. Swartz

Publisher: Elsevier Science
Year: 1977
Tongue: English
Weight: 497 KB
Volume: 23
Category: Article
ISSN: 0020-1693
DOI: 10.1016/s0020-1693(00)94765-0

No coin nor oath required. For personal study only.

✦ Synopsis

The reaction of toluene solutions of FeTPPCl with RSH (R = CH3 or (CH&') in the presence of pyridine has been studied by epr and electronic spectra. The reaction results in the reduction of FeTPPCl to FeTPP(Py)2 and the oxidation of RSH to R&. Kinetic data obtained for the reaction shows the observed rate law to be: -d[FeTPPCl]/dt = k[FeTPPCI](RSH]fPy] 3 Epr studies show the involvement of two paramagnetic, S = I/2, intermediates. The first intermediate is assigned as FeTPP(pY)(SR), while the second intermediate is postulated as FeTPP(Py),(RS). Possible structures for this second intermediate are discussed.

A mechanism is proposed which is consistant with the observed data. The autocatalytic nature of this system is also described.

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