Merging Organometallic Chemistry with Polyoxometalate Chemistry

Gouzerh, Pierre; Villanneau, Richard; Delmont, Renaud; Proust, Anna

doi:10.1002/(sici)1521-3765(20000403)6:7<1184::aid-chem1184>3.0.co;2-b

Cited by 38 publications

(6 citation statements)

References 73 publications

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“…This new polyoxoanion can be considered as grafting four [Mn(CO) 3 ] + pendants onto the previous unreported selenotungstate fragment [Se 2 W 11 O 43 ] 8– via five μ 3 -O atoms (O4, O17, O26, O35, O39) and six μ 2 -O atoms (O9, O24, O27, O30, O32, O37) (Figure S1). All the Mn–C and C–O bond lengths are in the ranges of 1.753–1.903 Å and 1.093–1.193 Å, respectively, and the Mn–C/C–O bonds lengths are equal within experimental errors …”

Section: Resultsmentioning

confidence: 88%

Facile CO₂ Cycloaddition to Epoxides by Using a Tetracarbonyl Metal Selenotungstate Derivate [{Mn(CO)₃}₄(Se₂W₁₁O₄₃)]^8–

Singh

et al. 2018

Inorg. Chem.

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A novel polyoxometalate cluster, i.e., Na 1.5 H 4.5 [(CH 3 ) 4 N] 2 {[Mn(CO) 3 ] 4 (Se 2 W 11 O 43 )}•9H 2 O (1), has been successfully synthesized under moderately acidic conditions. Compound 1 contains four electron-donating {Mn(CO) 3 } + organometallic entities, which are grafted over an unprecedented heteropolytungstate electron-acceptor group. Compound 1 was further structurally characterized by various physicochemical techniques like elemental analyses, inductively coupled plasma (ICP) analyses, IR and UV−vis spectroscopy, electrochemistry, and single-crystal X-ray diffraction, and so on. The polyoxoanion of 1 comprises a novel {Se 2 W 11 } fragment, which is obtained from molecular assembly of rare {SeW 3 } and {SeW 8 } species. Evaluation of the data from solution-state IR spectrum showed excellent agreement with the solid state IR spectrum, indicating the intact clusters in the CH 3 CN/Na 2 SO 4 solvent. Also, negative electrospray ionization mass spectrometry (ESI-MS) was an alternative tool to verify the stability of 1 in the mixed solvent. Additionally, the resulting hybrid can act as a catalyst for cyclic carbonate formation from the reactants epoxides and CO 2 under modest reaction conditions in conjunction with a 1-ethyl-1-methylpyrrolidinium bromide (2). The good activity can be substantiated due to the cooperative influence of polyoxoanion and Br − ions. Complex 1 can also be easily recycled and reused three times without obvious decrease of catalytic activity.

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Section: Resultsmentioning

confidence: 88%

Facile CO₂ Cycloaddition to Epoxides by Using a Tetracarbonyl Metal Selenotungstate Derivate [{Mn(CO)₃}₄(Se₂W₁₁O₄₃)]^8–

Singh

et al. 2018

Inorg. Chem.

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“…Finally, it has been shown that a Na 12 [(WZnZn 2 (H 2 O) 2 ]-[(ZnW 9 O 34 ) 2 ] assembled in situ in water is a very effective catalyst for oxidation of alcohols with hydrogen peroxide in aqueous biphasic media. 22 Polyoxometalate based hybrid compounds 23 have been constructed either by formation of covalent bonds between organic and inorganic moieties or by creation of electrostatic interactions 24 between the inorganic and organic components. Polyoxometalates are also important as building units of supramolecular complexes since they can exhibit diverse self-assembly properties for such supramolecular materials, thus controlling the formation of n-dimensional organic-inorganic hybrid networks in self-organization processes.…”

Section: Introductionmentioning

confidence: 99%

New Heterogeneous Polyoxometalate Based Mesoporous Catalysts for Hydrogen Peroxide Mediated Oxidation Reactions

2003

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Inorganic-organic hybrid mesoporous materials were prepared by cocrystallization of a "sandwich" type polyoxometalate, [ZnWZn2(H2O)2(ZnW9O34)2]12-, and branched tripodal organic polyammonium salts, tris[2-(trimethylammonium)ethyl]-1,3,5-benzenetricarboxylate or 1,3,5-tris[4-(N,N,N-trimethylammoniumethylcarboxyl)phenyl]benzene trications. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed formation of three-dimensional perforated coral-shaped amorphous materials with the organic cations surrounding polyoxometalate anions. N2 sorption analysis showed that the hybrid materials have a BET surface area of approximately 30-50 m2 g(-1) and an average pore diameter of 36 A leading to the classification of these materials as mesoporous materials with moderate surface areas. These hybrid materials behaved as very effective and selective heterogeneous catalysts for the epoxidation of allylic alcohols and oxidation of secondary alcohols to ketones with hydrogen peroxide as oxidant. The activity and selectivity of the heterogeneous catalysts based on the hybrid materials was similar to those of homogeneous catalysts based on the same [ZnWZn1(H2O)2(ZnW9O34)2]12- polyoxometalate.

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“…However, the effect of this delicate tuning on the potential-induced redox switching of the surface-confined POM core has not yet been studied. In particular, the transition from peripheral ligand post-functionalisation by organic moieties 19–22 to that by electronically active organometallic complexes 23,24 is of great interest from the point of view of creating functional hybrid electron transport ensembles.…”

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confidence: 99%

Increasing the redox switching capacity of Lindqvist-type hexavanadates by organogold post-functionalisation

et al. 2023

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Merging Organometallic Chemistry with Polyoxometalate Chemistry

Cited by 38 publications

References 73 publications

Facile CO₂ Cycloaddition to Epoxides by Using a Tetracarbonyl Metal Selenotungstate Derivate [{Mn(CO)₃}₄(Se₂W₁₁O₄₃)]^8–

Facile CO₂ Cycloaddition to Epoxides by Using a Tetracarbonyl Metal Selenotungstate Derivate [{Mn(CO)₃}₄(Se₂W₁₁O₄₃)]^8–

New Heterogeneous Polyoxometalate Based Mesoporous Catalysts for Hydrogen Peroxide Mediated Oxidation Reactions

Increasing the redox switching capacity of Lindqvist-type hexavanadates by organogold post-functionalisation

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Merging Organometallic Chemistry with Polyoxometalate Chemistry

Cited by 38 publications

References 73 publications

Facile CO2 Cycloaddition to Epoxides by Using a Tetracarbonyl Metal Selenotungstate Derivate [{Mn(CO)3}4(Se2W11O43)]8–

Facile CO2 Cycloaddition to Epoxides by Using a Tetracarbonyl Metal Selenotungstate Derivate [{Mn(CO)3}4(Se2W11O43)]8–

New Heterogeneous Polyoxometalate Based Mesoporous Catalysts for Hydrogen Peroxide Mediated Oxidation Reactions

Increasing the redox switching capacity of Lindqvist-type hexavanadates by organogold post-functionalisation

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Facile CO₂ Cycloaddition to Epoxides by Using a Tetracarbonyl Metal Selenotungstate Derivate [{Mn(CO)₃}₄(Se₂W₁₁O₄₃)]^8–

Facile CO₂ Cycloaddition to Epoxides by Using a Tetracarbonyl Metal Selenotungstate Derivate [{Mn(CO)₃}₄(Se₂W₁₁O₄₃)]^8–