A ruthenium-substituted polyoxometalate as an inorganic dioxygenase for activation of molecular oxygen

Neumann, Ronny; Dahan, Mazal

doi:10.1038/41039

Cited by 354 publications

(155 citation statements)

References 13 publications

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“…[78,79] These complexes, as tricaprylammonium salts, especially the cobaltfree species, were found to catalyze the hydroxylation of adamantane at the tertiary position using dioxygen at autogenous pressure. [79][80][81] The process was mentioned to function in a dioxygenase-like fashion incorporating both oxygen atoms of O 2 into two substrate molecules, [80] but this claim has been disputed in favor of a classical autoxidation mechanism. [82] The same POM has also been shown to catalyze various epoxidation and oxidation reactions in different media, as well as under biphasic conditions.…”

Section: Rutheniummentioning

confidence: 99%

Noble Metals in Polyoxometalates

2012

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Polyoxometalates containing noble metal ions, such as ruthenium, osmium, rhodium, palladium, platinum, silver and gold, are a structurally diverse class of compounds. They include both classical heteropolyanions (vanadates, molybdates, tungstates) in which noble metals are present as heteroatoms, as well as the recently discovered class of polyoxometalates with noble metal "addenda" atoms. The focus of this Review is on complexes that should, in principle, exist as discrete molecular species in solution, and which are therefore of interest for their reactivity, their future synthetic utility and potential applications, for example, in catalysis or nanoscience.

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Section: Rutheniummentioning

confidence: 99%

Noble Metals in Polyoxometalates

2012

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“…[7,8] Many challenges are associated with the realization of these goals due to difficulties with oxygen and substrate activation for the oxidation of alkanes. [9,10] To date, only a few catalytic systems have been reported for the liquid-phase oxidation of alkanes using air, but most are in combination with additives and solvents or are preformed under severe conditions (high pressure).…”

Section: -A C H T U N G T R E N N U N G (H 2 O) 12 (P 8 W 48 O 184 )]mentioning

confidence: 99%

“…[9,10] To date, only a few catalytic systems have been reported for the liquid-phase oxidation of alkanes using air, but most are in combination with additives and solvents or are preformed under severe conditions (high pressure). [7][8][9]11] Polyoxometalates (POMs) are a unique class of metaloxygen clusters with a diverse compositional range and an enormous structural variety. [12] Although this class of POMs was discovered by Berzelius almost 200 years ago, the systematic structural design of novel POMs and derivation of known POMs remains a major challenge for synthetic chemists.…”

Section: -A C H T U N G T R E N N U N G (H 2 O) 12 (P 8 W 48 O 184 )]mentioning

confidence: 99%

Heterogeneous Wheel‐Shaped Cu₂₀‐Polyoxotungstate [Cu₂₀Cl(OH)₂₄(H₂O)₁₂(P₈W₄₈O₁₈₄)]²⁵⁻ Catalyst for Solvent‐Free Aerobic Oxidation of n‐Hexadecane

Chen

Mal

et al. 2009

Chemistry A European J

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The selective oxidation of alkanes as a green process remains a challenging task because partial oxidation is easier to achieve with sacrificial oxidants, such as hydrogen peroxide, alkyl hydroperoxides or iodosylbenzene, than with molecular oxygen or air. Here, we report on a heterogeneous catalyst for n-hexadecane oxidation comprised of the wheel shaped Cu20-polyoxotungstate [Cu20Cl(OH)24(H2O)12(P8W48O184)]25- anchored on 3-aminopropyltriethoxysilane (apts)-modified SBA-15. The catalysts were characterized by powder X-ray diffraction (XRD), N2-adsorption measurements and Fourier transform infrared reflectance (FT-IR) spectroscopy. The heterogeneous Cu20-polyanion system catalyzed the solvent-free aerobic oxidation of n-hexadecane to alcohols and ketones by using air as the oxidant under ambient conditions. The catalyst exhibits an exceptionally high turn over frequency (TOF) of 20,000 h(-1) at 150 degrees C and is resistant to poisoning by CS2. Moreover, it can be easily recovered and reused by filtration without loss of its catalytic activity. Possible homogeneous contributions also have been examined and eliminated. Thus, this system can use air as oxidant, which, in combination with its good overall performance and poison tolerance, raises the prospect of this type of heterogeneous catalyst for practical applications.

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“…This inaugurated new directions in synthesis, leading to an explosion in reports of a variety of compounds for use in an expanding range of applications. This tendency was supported by the fact that POM reduction potentials, acidities, and other properties are relevant, for example, for green chemistry, [8] renewable energy (Figure 3), [9][10][11] or catalysis [12,13] (model compounds are also considered [14] ). Parallel to the above developments, the discovery of giant molybdenum/tungsten oxide clusters (obtained under reducing conditions according to a type of growth process) containing up to 368 metal atoms [15] was considered by the scientific community as a breakthrough because it was the route to new length scales and provided the option to discover a variety of new phenomena, including those related to processes under confined conditions.…”

mentioning

confidence: 86%

Oxo‐Metalate Building Blocks: Conceptual Competitors for Tetravalent Carbon?

Weinstock¹,

Müller²

2011

Israel Journal of Chemistry

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In honor of Prof. Michael T. Pope for over half a century of excellent contributions to polyoxometalate chemistryThe versatility of chemistry based on tetravalent carbon is unparalleled. Small organic molecules are readily modifiable by traditional serial syntheses and/or combinatorial libraries, and systematically linked together by Nature; in the laboratory, polymeric structures ranging from biological macromolecules to functional solid-state materials can be generated. Meanwhile, molecular or oligomeric building blocks can be designed to self-assemble into supramolecular structures, including increasingly sophisticated "nano-reactors" [1,2] that link molecular to nano-scale worlds. When combined with metal cations, organic linkers can generate (now predictable) metal-organic frameworks (MOFs) with large and controllable pore sizes. [3] On the other hand in 1991, Pope and Müller noted in a review that metal oxide cluster anions (polyoxometalates, or POMs) "form a class of inorganic compounds that is unmatched in terms of molecular and electronic structural versatility, reactivity, and relevance to analytical chemistry, catalysis, biology, medicine, geochemistry, materials science, and topology."

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A ruthenium-substituted polyoxometalate as an inorganic dioxygenase for activation of molecular oxygen

Cited by 354 publications

References 13 publications

Noble Metals in Polyoxometalates

Noble Metals in Polyoxometalates

Heterogeneous Wheel‐Shaped Cu₂₀‐Polyoxotungstate [Cu₂₀Cl(OH)₂₄(H₂O)₁₂(P₈W₄₈O₁₈₄)]²⁵⁻ Catalyst for Solvent‐Free Aerobic Oxidation of n‐Hexadecane

Oxo‐Metalate Building Blocks: Conceptual Competitors for Tetravalent Carbon?

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A ruthenium-substituted polyoxometalate as an inorganic dioxygenase for activation of molecular oxygen

Cited by 354 publications

References 13 publications

Noble Metals in Polyoxometalates

Noble Metals in Polyoxometalates

Heterogeneous Wheel‐Shaped Cu20‐Polyoxotungstate [Cu20Cl(OH)24(H2O)12(P8W48O184)]25− Catalyst for Solvent‐Free Aerobic Oxidation of n‐Hexadecane

Oxo‐Metalate Building Blocks: Conceptual Competitors for Tetravalent Carbon?

Contact Info

Product

Resources

About

Heterogeneous Wheel‐Shaped Cu₂₀‐Polyoxotungstate [Cu₂₀Cl(OH)₂₄(H₂O)₁₂(P₈W₄₈O₁₈₄)]²⁵⁻ Catalyst for Solvent‐Free Aerobic Oxidation of n‐Hexadecane