A 31P-NMR study of peroxo species formed during oxidation of cyclohexene with hydrogen peroxide in tri-n-butylphosphate catalyzed by heteropolyacids

Masato Hashimoto; Koshi Itoh; Kwan Young Lee; Makoto Misono

doi:10.1023/a:1016600601054

A ³¹P-NMR study of peroxo species formed during oxidation of cyclohexene with hydrogen peroxide in tri-n-butylphosphate catalyzed by heteropolyacids

Masato Hashimoto, Koshi Itoh, Kwan Young Lee, Makoto Misono

Research output: Contribution to journal › Article › peer-review

19 Citations (Scopus)

Abstract

In the oxidation of cyclohexene with H₂O₂ in monophasic tri-n-butylphosphate (TBP) solution catalyzed by Keggin-type 12-heteropolyacids, i.e., H₃PMo_12-xW_xO₄₀ (x = 0-12), several peroxo species were observed by ³¹P-NMR spectroscopy in lower field than the original heteropolyacids. Their composition varied regularly with that of the starting catalyst. The P-containing peroxo species formed was deduced as [PM₄O₈(O₂)₈]^3- (M = Mo, W). The peroxo species formed more easily with a decrease in the W content, x of H₃PMo_12-xW_xO₄₀). It was further indicated from the reactivity with cyclohexene and the comparison with catalytic performance that W-rich peroxo species were catalytically more active than Mo-rich peroxo species for the oxidation of cyclohexene in this reaction system.

Original language	English
Pages (from-to)	265-271
Number of pages	7
Journal	Topics in Catalysis
Volume	15
Issue number	2-4
DOIs	https://doi.org/10.1023/a:1016600601054
Publication status	Published - 2001

Keywords

Heteropoly catalyst
Olefin oxidation
P-NMR
Peroxopolyoxometalates

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1023/a:1016600601054

Cite this

@article{787c226665bf476ea23a0a93b5e73f22,

title = "A 31P-NMR study of peroxo species formed during oxidation of cyclohexene with hydrogen peroxide in tri-n-butylphosphate catalyzed by heteropolyacids",

abstract = "In the oxidation of cyclohexene with H2O2 in monophasic tri-n-butylphosphate (TBP) solution catalyzed by Keggin-type 12-heteropolyacids, i.e., H3PMo12-xWxO40 (x = 0-12), several peroxo species were observed by 31P-NMR spectroscopy in lower field than the original heteropolyacids. Their composition varied regularly with that of the starting catalyst. The P-containing peroxo species formed was deduced as [PM4O8(O2)8]3- (M = Mo, W). The peroxo species formed more easily with a decrease in the W content, x of H3PMo12-xWxO40). It was further indicated from the reactivity with cyclohexene and the comparison with catalytic performance that W-rich peroxo species were catalytically more active than Mo-rich peroxo species for the oxidation of cyclohexene in this reaction system.",

keywords = "Heteropoly catalyst, Olefin oxidation, P-NMR, Peroxopolyoxometalates",

author = "Masato Hashimoto and Koshi Itoh and Lee, {Kwan Young} and Makoto Misono",

year = "2001",

doi = "10.1023/a:1016600601054",

language = "English",

volume = "15",

pages = "265--271",

journal = "Topics in Catalysis",

issn = "1022-5528",

publisher = "Springer",

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T1 - A 31P-NMR study of peroxo species formed during oxidation of cyclohexene with hydrogen peroxide in tri-n-butylphosphate catalyzed by heteropolyacids

AU - Hashimoto, Masato

AU - Itoh, Koshi

AU - Lee, Kwan Young

AU - Misono, Makoto

PY - 2001

Y1 - 2001

N2 - In the oxidation of cyclohexene with H2O2 in monophasic tri-n-butylphosphate (TBP) solution catalyzed by Keggin-type 12-heteropolyacids, i.e., H3PMo12-xWxO40 (x = 0-12), several peroxo species were observed by 31P-NMR spectroscopy in lower field than the original heteropolyacids. Their composition varied regularly with that of the starting catalyst. The P-containing peroxo species formed was deduced as [PM4O8(O2)8]3- (M = Mo, W). The peroxo species formed more easily with a decrease in the W content, x of H3PMo12-xWxO40). It was further indicated from the reactivity with cyclohexene and the comparison with catalytic performance that W-rich peroxo species were catalytically more active than Mo-rich peroxo species for the oxidation of cyclohexene in this reaction system.

AB - In the oxidation of cyclohexene with H2O2 in monophasic tri-n-butylphosphate (TBP) solution catalyzed by Keggin-type 12-heteropolyacids, i.e., H3PMo12-xWxO40 (x = 0-12), several peroxo species were observed by 31P-NMR spectroscopy in lower field than the original heteropolyacids. Their composition varied regularly with that of the starting catalyst. The P-containing peroxo species formed was deduced as [PM4O8(O2)8]3- (M = Mo, W). The peroxo species formed more easily with a decrease in the W content, x of H3PMo12-xWxO40). It was further indicated from the reactivity with cyclohexene and the comparison with catalytic performance that W-rich peroxo species were catalytically more active than Mo-rich peroxo species for the oxidation of cyclohexene in this reaction system.

KW - Heteropoly catalyst

KW - Olefin oxidation

KW - P-NMR

KW - Peroxopolyoxometalates

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