Kinetics and mechanism of oxygen transfer to methyloxo(dithiolato)rhenium(V) complexes

G. Lente, J. H. Espenson

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24 Citations (Scopus)

Abstract

The kinetics and mechanism of the reactions of the dimeric and monomeric methyloxo(dithiolato)rhenium(V) complexes [(o-SC6H4CH2S)Re(O)CH3]2 and [(o-SC6H4CH2S)PyRe(O)CH3] (Py = pyridine) with XO, sulfoxides, and pyridine N-oxides are studied. In these reactions, an oxygen atom from XO is transferred to rhenium, from which it later removed. A reaction scheme is proposed to interpret the kinetic data. This scheme features the formation of a monomeric (sulfoxide)- or (pyridine N-oxide)(dithiolato)methyloxorhenium(V) complex followed by its bimolecular oxidation in a rate-controlling step. Several sulfoxides (methyl, methyl phenyl, and substituted diphenyl) all react at similar rates. Activation parameters are determined for dimethyl sulfoxide and di-4-tolyl sulfoxide from temperature-dependent studies. The reactions with pyridine N-oxides show autocatalysis in which the catalyst is confirmed to be pyridine formed in the reactions.

Original languageEnglish
Pages (from-to)4809-4814
Number of pages6
JournalInorganic Chemistry
Volume39
Issue number21
DOIs
Publication statusPublished - Oct 16 2000

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sulfoxide
Rhenium
rhenium
Sulfoxides
pyridines
Oxygen
Kinetics
kinetics
oxygen
oxides
Dimethyl Sulfoxide
autocatalysis
Chemical activation
Atoms
Oxidation
Catalysts
oxygen atoms
pyridine N-oxide
oligomycin sensitivity-conferring protein
activation

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Kinetics and mechanism of oxygen transfer to methyloxo(dithiolato)rhenium(V) complexes. / Lente, G.; Espenson, J. H.

In: Inorganic Chemistry, Vol. 39, No. 21, 16.10.2000, p. 4809-4814.

Research output: Contribution to journalArticle

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N2 - The kinetics and mechanism of the reactions of the dimeric and monomeric methyloxo(dithiolato)rhenium(V) complexes [(o-SC6H4CH2S)Re(O)CH3]2 and [(o-SC6H4CH2S)PyRe(O)CH3] (Py = pyridine) with XO, sulfoxides, and pyridine N-oxides are studied. In these reactions, an oxygen atom from XO is transferred to rhenium, from which it later removed. A reaction scheme is proposed to interpret the kinetic data. This scheme features the formation of a monomeric (sulfoxide)- or (pyridine N-oxide)(dithiolato)methyloxorhenium(V) complex followed by its bimolecular oxidation in a rate-controlling step. Several sulfoxides (methyl, methyl phenyl, and substituted diphenyl) all react at similar rates. Activation parameters are determined for dimethyl sulfoxide and di-4-tolyl sulfoxide from temperature-dependent studies. The reactions with pyridine N-oxides show autocatalysis in which the catalyst is confirmed to be pyridine formed in the reactions.

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