Catalytic oxidative ring opening of THF promoted by a carboxylate-bridged diiron complex, triarylphosphines, and dioxygen

Rayane F. Moreira; Edit Y. Tshuva; Stephen J. Lippard

doi:10.1021/ic049460+

Catalytic oxidative ring opening of THF promoted by a carboxylate-bridged diiron complex, triarylphosphines, and dioxygen

Rayane F. Moreira
, Edit Y. Tshuva
, Stephen J. Lippard^*

^*Corresponding author for this work

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

49 Scopus citations

Abstract

The catalytic oxidation of triphenylphosphine in the presence of dioxygen by the diiron(II) complex [Fe₂(μ-O₂- CAr ^Tol)₂(Me₃TACN)₂(MeCN) ₂](OTf)₂ (1), where ^-O₂CAr ^Tol = 2,6-di(p-tolyl)benzoate and Me₃TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane, has been investigated. The corresponding diiron(III) complex, [Fe₂(μ-O)(μ-O ₂CAr^Tol)₂(Me₃-TACN) ₂](OTf)₂ (2), the only detectable iron-containing species during the course of the reaction, can itself promote the reaction. Phosphine oxidation is coupled to the catalytic oxidation of THF solvent to afford, selectively, the C-C bond-cleavage product 3-hydroxypropylformate, an unprecedented transformation. After consumption of the phosphine, solvent oxidation continues but results in the products 2-hydroperoxytetrahydrofuran, butyrolactone, and butyrolactol. The similarities of the reaction pathways observed in the presence and absence of catalyst, as well as ¹⁸O labeling, solvent dependence, and radical probe experiments, provide evidence that the oxidation is initiated by a metal-centered H-atom abstraction from THF. A mechanism for catalysis is proposed that accounts for the coupled oxidation of the phosphine and the THF ring-opening reaction.

Original language	English
Pages (from-to)	4427-4434
Number of pages	8
Journal	Inorganic Chemistry
Volume	43
Issue number	14
DOIs	https://doi.org/10.1021/ic049460+
State	Published - 12 Jul 2004
Externally published	Yes

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@article{25a568c1d5ca4720b91169f04a126981,

title = "Catalytic oxidative ring opening of THF promoted by a carboxylate-bridged diiron complex, triarylphosphines, and dioxygen",

abstract = "The catalytic oxidation of triphenylphosphine in the presence of dioxygen by the diiron(II) complex [Fe2(μ-O2- CAr Tol)2(Me3TACN)2(MeCN) 2](OTf)2 (1), where -O2CAr Tol = 2,6-di(p-tolyl)benzoate and Me3TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane, has been investigated. The corresponding diiron(III) complex, [Fe2(μ-O)(μ-O 2CArTol)2(Me3-TACN) 2](OTf)2 (2), the only detectable iron-containing species during the course of the reaction, can itself promote the reaction. Phosphine oxidation is coupled to the catalytic oxidation of THF solvent to afford, selectively, the C-C bond-cleavage product 3-hydroxypropylformate, an unprecedented transformation. After consumption of the phosphine, solvent oxidation continues but results in the products 2-hydroperoxytetrahydrofuran, butyrolactone, and butyrolactol. The similarities of the reaction pathways observed in the presence and absence of catalyst, as well as 18O labeling, solvent dependence, and radical probe experiments, provide evidence that the oxidation is initiated by a metal-centered H-atom abstraction from THF. A mechanism for catalysis is proposed that accounts for the coupled oxidation of the phosphine and the THF ring-opening reaction.",

author = "Moreira, \{Rayane F.\} and Tshuva, \{Edit Y.\} and Lippard, \{Stephen J.\}",

year = "2004",

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doi = "10.1021/ic049460+",

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AU - Moreira, Rayane F.

AU - Tshuva, Edit Y.

AU - Lippard, Stephen J.

PY - 2004/7/12

Y1 - 2004/7/12

N2 - The catalytic oxidation of triphenylphosphine in the presence of dioxygen by the diiron(II) complex [Fe2(μ-O2- CAr Tol)2(Me3TACN)2(MeCN) 2](OTf)2 (1), where -O2CAr Tol = 2,6-di(p-tolyl)benzoate and Me3TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane, has been investigated. The corresponding diiron(III) complex, [Fe2(μ-O)(μ-O 2CArTol)2(Me3-TACN) 2](OTf)2 (2), the only detectable iron-containing species during the course of the reaction, can itself promote the reaction. Phosphine oxidation is coupled to the catalytic oxidation of THF solvent to afford, selectively, the C-C bond-cleavage product 3-hydroxypropylformate, an unprecedented transformation. After consumption of the phosphine, solvent oxidation continues but results in the products 2-hydroperoxytetrahydrofuran, butyrolactone, and butyrolactol. The similarities of the reaction pathways observed in the presence and absence of catalyst, as well as 18O labeling, solvent dependence, and radical probe experiments, provide evidence that the oxidation is initiated by a metal-centered H-atom abstraction from THF. A mechanism for catalysis is proposed that accounts for the coupled oxidation of the phosphine and the THF ring-opening reaction.

AB - The catalytic oxidation of triphenylphosphine in the presence of dioxygen by the diiron(II) complex [Fe2(μ-O2- CAr Tol)2(Me3TACN)2(MeCN) 2](OTf)2 (1), where -O2CAr Tol = 2,6-di(p-tolyl)benzoate and Me3TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane, has been investigated. The corresponding diiron(III) complex, [Fe2(μ-O)(μ-O 2CArTol)2(Me3-TACN) 2](OTf)2 (2), the only detectable iron-containing species during the course of the reaction, can itself promote the reaction. Phosphine oxidation is coupled to the catalytic oxidation of THF solvent to afford, selectively, the C-C bond-cleavage product 3-hydroxypropylformate, an unprecedented transformation. After consumption of the phosphine, solvent oxidation continues but results in the products 2-hydroperoxytetrahydrofuran, butyrolactone, and butyrolactol. The similarities of the reaction pathways observed in the presence and absence of catalyst, as well as 18O labeling, solvent dependence, and radical probe experiments, provide evidence that the oxidation is initiated by a metal-centered H-atom abstraction from THF. A mechanism for catalysis is proposed that accounts for the coupled oxidation of the phosphine and the THF ring-opening reaction.

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ER -

Catalytic oxidative ring opening of THF promoted by a carboxylate-bridged diiron complex, triarylphosphines, and dioxygen

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