Oxidation of thioanisoles and methyl phenyl sulfoxides by oxo(phosphine)ruthenium(IV) complexes

Journal Article · Wed Jan 20 04:00:00 EST 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00054a008· OSTI ID:7073353

Acquaye, J H; Muller, J G; Takeuchi, K J ^[1]

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1. State Univ. of New York, Buffalo (United States)

The oxo(phosphine)ruthenium(IV) complexes [Ru(bpy)[sub 2](O)PR[sub 3]](ClO[sub 4])[sub 2] (bpy = 2,2[prime]-bipyridine; PR[sub 3] = P(C[sub 6]H[sub 5])[sub 3], P(p-C[sub 6]H[sub 4]OCH[sub 3])[sub 3], P(p-C[sub 6]H[sub 4]CH[sub 3])[sub 3], P(p-C[sub 6]H[sub 4]F)[sub 3], P(C[sub 6]H[sub 5])(p-C[sub 6]H[sub 4]CF[sub 3])[sub 2], P(p-C[sub 6]H[sub 4]CF[sub 3])[sub 3]) cleanly oxidize sulfides to sulfoxides and in separate experiments oxidize sulfoxides to sulfones. The substrate oxidations are second order overall, first order in substrate concentration and first order in ruthenium concentration. Through the use of para-substituted thioanisoles and para-substituted methyl phenyl sulfoxides, linear free energy relationship analyses of the kinetics of substrate oxidations by [Ru(bpy)[sub 2](O)P(C[sub 6]H[sub 5])[sub 3]](ClO[sub 4])[sub 2] were conducted. For the oxidation of sulfides to sulfoxides, an excellent correlation (R[sup 2] = 0.99) was obtained between log (k[sub X]/k[sub H]) and the [sigma][sup [minus]] values for the substituents of para-substituted thioanisoles ([rho] = [minus]1.56). For the oxidation of sulfoxides to sulfones, a good correlation (R[sup 2] = 0.98) was obtained between log (k[sub X]/k[sub H]) and the [sigma][sup +] values for the substituents of para-substituted methyl phenyl sulfoxides ([rho] = [minus]0.42). 57 refs., 8 figs., 2 tabs.

• OSTI ID: 7073353
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:2; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
AZINES
BIPYRIDINES
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DATA
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
ISOTOPE EFFECTS
KINETICS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDATION
PHOSPHINES
PHOSPHORUS COMPOUNDS
PYRIDINES
REACTION KINETICS
REDUCTION
RESONANCE
RUTHENIUM COMPLEXES
SPECTRA
SPECTROSCOPY
SULFIDES
SULFOXIDES
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPLEXES
VISIBLE SPECTRA