Facile abstraction of successive oxygen atoms from perchlorate ions by methylrhenium dioxide

Journal Article · Wed Dec 06 04:00:00 EST 1995 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic00129a005· OSTI ID:457079

Abu-Omar, M M; Espenson, J H ^[1]

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1. Iowa State Univ., Ames, IA (United States)

Perchlorate ions are notoriously sluggish oxidizing agents. We have found that methylrhenium dioxide (CH{sub 3}ReO{sub 2}, or MDO), prepared in situ from CH{sub 3}ReO{sub 3} (MTO) and H{sub 3-}PO{sub 2}, reacts efficiently with ClO{sub 4}{sup -} in aqueous solution at pH 0 (1.0 M HOTf, trifluoromethanesulfonic acid). The occurrence of this reaction was established by the following experiments. (a) Addition of ClO{sub 4}{sup -} to a solution of MDO caused the regeneration of the UV and {sup 1}H spectra of MTO, at the same concentration that existed prior to the formation of MDO, with due allowance for the dilution (b) Aged solutions of MDO turned blue as the dinuclear species MeO{sub 2}Re-O-ReO{sub 2}Me was formed from MDO and MTO, and eventually a black precipitate deposited, this being the dimer and oligomers of MDO; addition of ClO{alpha}{sub 4}{sup -} at either state restored MTO quantitatively, showing that the methyl-rhenium bond remained intact in these species. (c) Tests for chloride in the final solutions were positive: both a qualitative test, precipitation of AgCl, as well as quantitative detection by ion chromatography. (d) MTO was also regenerated by adding ClO{sub 3}{sup -} to the MDO solutions, more rapidly than with ClO{sub 4}{sup -}. (e) Conduct of the MTO-H{sub 3}PO{sub 2} reaction in 0.1 M perchloric acid gave, by UV and {sup 1}H-NMR, the appearance that no reaction had occurred; in fact, these methods were unresponsive to the conversion of ClO{sub 4}{sup -} to Cl{sup -} as the cycle of reactions caused MTO to remain at a constant concentration. (f) Nevertheless, when the reaction in (e) was monitored by {sup 31}P-NMR, clear evidence was obtained for the formation of H{sub 3-}PO{sub 3}.

• Sponsoring Organization: USDOE
• OSTI ID: 457079
• Journal Information: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 25 Vol. 34; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
OXIDIZERS
PERCHLORATES
RHENIUM OXIDES