Studies on transition-metal oxo and nitrido complexes. 13. Perruthenate and ruthenate anions as catalytic organic oxidants

Journal Article · Wed Feb 03 04:00:00 EST 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00055a006· OSTI ID:6709318

Bailey, A J; Griffith, W P; Mostafa, S I; Sherwood, P A ^[1]

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1. Imperial College of Science, London (United Kingdom)

Oxo complexes of ruthenium are effective catalysts for the selective oxidation of various organic substrates. Thus the ruthenate ion trans-[Ru(OH)[sub 2]O[sub 3]][sup 2[minus]], which is stable above pH 12 in aqueous base, with persulfate as cooxidant will oxidize primary alcohols to carboxylic acids and secondary alcohols to ketones, the perruthenate ion [RuO[sub 4]][sup [minus]], which is stable from pH 8 to 12 in aqueous base, will also effect such oxidations stoichiometrically in solution. The organic-soluble TPAP' ((n-Pr[sub 4]N)[RuO[sub 4]]) with N-methylmorpholine N-oxide is an efficient selective catalyst for converting primary alcohols to aldehydes and secondary alcohols to ketones. The [RuO[sub 4]][sup [minus]] ion can be generated in aqueous base at pH 11 from aquated ruthenium trichloride with excess bromate, and this reagent will catalytically oxidize primary alcohols, activated alkyl halides, aldehydes, 1,2-diols, and nitroalkanes to carboxylic acids, while secondary alcohols and secondary halides are oxidized to ketones, bromate being the cooxidant. These oxidations are compared with those effected catalytically by trans-[Ru(OH)[sub 2]O[sub 3]][sup 2[minus]] in aqueous base at pH 14 with persulfate as cooxidant. A new preparation for organic-soluble salts of [RuO[sub 4]][sup [minus]] avoiding the use of RuO[sub 4] is described. 29 refs., 1 tab.

• OSTI ID: 6709318
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:3; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALCOHOLS
ALDEHYDES
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
GLYCOLS
HOMOGENEOUS CATALYSIS
HYDROGEN COMPOUNDS
HYDROXIDES
HYDROXY COMPOUNDS
NITRO COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
OXIDES
OXYGEN COMPOUNDS
PH VALUE
REFRACTORY METAL COMPOUNDS
RUTHENIUM COMPOUNDS
RUTHENIUM HYDROXIDES
RUTHENIUM OXIDES
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS