Microwave synthesis of hybrid inorganic–organic materials including porous Cu3(BTC)2 from Cu(II)-trimesate mixture

RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required according to the journal that you are submitting your paper to) TITLE RUNNING HEAD Kinetics of the Lewis acid catalyzed citronellal cyclization 2 ABSTRACT Industrial (-)-menthol production generally relies on the hydrogenation of (-)-isopulegol, which is in turn produced with high selectivity by cyclization of (+)-citronellal. This paper uses a combined theoretical and experimental approach to study the activity and selectivity of three Lewis acid catalysts for this reaction, namely ZnBr 2 , aluminum tris(2,6-diphenylphenoxide) (ATPH) and the heterogeneous metal-organic framework Cu 3 BTC 2 (BTC = benzene-1,3,5-tricarboxylate). ATPH is a strong Lewis acid homogeneous catalyst with bulky ligands which provides very high selectivities for the desired stereoisomer (> 99 %). The performance of the catalysts was evaluated as a function of temperature, which revealed that higher catalyst activity allows working at lower temperatures and improves the selectivity for isopulegol. The selectivity distribution is kinetically driven for ZnBr 2 and ATPH. The theoretical selectivity distributions rely on the determination of an extensive set of diastereomeric transition states, for which the differences in free energy have been calculated using a complementary set of ab initio techniques. Given the sensitivity of the selectivity to small Gibbs free energy differences, the agreement between experimental and theoretical selectivities is satisfactory. On basis of the obtained insights rational design of new catalysts may be obtained. As proof of concept, the hypothetical Cu 3 (BTC-(NO 2 ) 3 ) 2 Lewis catalyst -in which each phenyl hydrogen of the BTC ligand is replaced by a nitro group -is predicted to be very selective.

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“…Cu-BTC was synthesized in the microwave oven using a procedure published by Seo et al [77]. Two different solutions were made:…”

Section: Experimental Catalyst Preparationmentioning

confidence: 99%

Insight in the activity and diastereoselectivity of various Lewis acid catalysts for the citronellal cyclization

Vandichel

Vermoortele

Cottenie

et al. 2013

Journal of Catalysis

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“…As reported earlier by us, MOFs show a significant difference in porosity and crystallinity depending on the synthetic conditions and preparation method as well as purification procedure. 18,19 Microwave-assisted hydrothermal or solvothermal synthesis (MW) has significant advantages over CH synthesis because of rapid heating, faster kinetics, higher yield and better reproducibility. [19][20][21][22][23] In addition to this, it provides an efficient way to control particle size distribution, phase selectivity and macroscopic morphology in the synthesis of nanoporous materials.…”

Section: Introductionmentioning

confidence: 99%

“…18,19 Microwave-assisted hydrothermal or solvothermal synthesis (MW) has significant advantages over CH synthesis because of rapid heating, faster kinetics, higher yield and better reproducibility. [19][20][21][22][23] In addition to this, it provides an efficient way to control particle size distribution, phase selectivity and macroscopic morphology in the synthesis of nanoporous materials. [24][25][26] Despite these facts, there are only a few reports on the use of microwave for synthesis of porous coordination materials.…”

Section: Introductionmentioning

confidence: 99%

Microwave Synthesis of a Porous Metal-Organic Framework, Nickel(II) Dihydroxyterephthalate and its Catalytic Properties in Oxidation of Cyclohexene

Lee¹,

Halligudi²,

Jang³

et al. 2010

Bulletin of the Korean Chemical Society

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A porous coordination solid of nickel(II) dihydroxyterephthalate has been synthesized by the microwave-assisted (MW) method. The synthesized nickel(II) dihyroxylterephthalate was designated by the general formula of [Ni2(dhtp) (H2O)2]·8H2O (where, dhtp = 2,5-dihydroxyterephthalate, denoted by Ni-DHTP). The effect of microwave-irradiation temperature and time of irradiation on the porosity and morphological changes in the solids have also been investigated. The catalytic performance of Ni-DHTP synthesized by MW method has been studied in the oxidation of cyclohexene with aqueous H2O2, which gave cyclohexene oxide as the primary product and 2-cyclohexene-1-ol as a major product.

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“…The intensities of the C=O band and of the broad band are significantly weaker in the GL as a consequence of the partial removal of carboxyliccarbonylic functionalities upon the reductive treatment. In the ATR-IR spectrum on HKUST-1, the bands at 1645 and 1590 cm -1 and at 1450 and 1370 cm -1 correspond to the asymmetric and symmetric stretching vibrations of the carboxylate groups in BTC, respectively [45,89]. The features in the ATR-IR spectra of the composites are similar to those observed on HKUST-1: a remarkable difference, however, is the absence of the C=O bands in the composites ATR-IR spectra.…”

Section: Experimental and Discussionmentioning

confidence: 52%

Graphene-Like Layers from Unconventional Carbon Sources: New Perspectives on Hybrid Materials and π-system Synergisms

Capua

Gargiulo

AlfГЁ

2016

Eurasian Chem. Tech. J.

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We developed a new approach for producing graphene-like (GL) materials through a two-steps oxidation/reduction method starting from a nanostructured (high surface) carbon black, a versatile carbonaceous material prone to be structurally and chemically modified in quite mild wet conditions. Atomic Force Microscopy and zetapotential measurements allowed to model the assembling mechanisms and the role of hydrophobic interactions, demonstrating the possibility to easily tune the surface morphology. GL materials have been then employed in a large variety of hybrid materials for innovative applications, and characterized by chemical, electrical, structural and spectroscopic techniques. With Metal-Organic Frameworks, GL produced conducting composites with electrical conductivity tunable by changing the concentration of the parent materials; Eumelanin/GL and TiO 2 -nanoparticles/GL were also studied for photocatalysis and biosensors applications.

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Microwave synthesis of hybrid inorganic–organic materials including porous Cu3(BTC)2 from Cu(II)-trimesate mixture

Cited by 321 publications

References 43 publications

Insight in the activity and diastereoselectivity of various Lewis acid catalysts for the citronellal cyclization

Insight in the activity and diastereoselectivity of various Lewis acid catalysts for the citronellal cyclization

Microwave Synthesis of a Porous Metal-Organic Framework, Nickel(II) Dihydroxyterephthalate and its Catalytic Properties in Oxidation of Cyclohexene

Graphene-Like Layers from Unconventional Carbon Sources: New Perspectives on Hybrid Materials and π-system Synergisms

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