A DFT Study of the Conversion of CO<sub>2</sub>in Dimethylcarbonate Catalyzed by Sn(IV) Alkoxides

Renata, Costa; Rosenbach, Nilton; Mota, Cláudio J. A.

doi:10.5935/0103-5053.20140240

Cited by 3 publications

(13 citation statements)

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“…Such organotin-functionalized ordered mesoporous silica can be obtained by co-condensing [(MeO) 2 ClSi(CH 2 ) 3 SnCl 3 ], tetraethyl orthosilicate, and 1,4-bis(triethoxysilyl)benzene in acidic Pluronic 123 solution. Density functional theory (DFT) calculations of intermediates and transition states suggest the interaction of CO 2 with tin(IV) alkoxides of the type R 2 Sn(OCH 3 ) 2 (R = alkyl, Ph, halogen) to be controlled by the entropic term . The subsequent insertion of CO 2 into the Sn–OCH 3 bond is thermodynamically favorable.…”

Section: Carbon Dioxide As a Building Block For Chemical Structuresmentioning

confidence: 99%

“…Density functional theory (DFT) calculations of intermediates and transition states suggest the interaction of CO 2 with tin(IV) alkoxides of the type R 2 Sn(OCH 3 ) 2 (R = alkyl, Ph, halogen) to be controlled by the entropic term. 121 The subsequent insertion of CO 2 into the Sn−OCH 3 bond is thermodynamically favorable. The computed free energy of activation was smallest for the substituent R being Ph groups.…”

Section: Organic Carbonatesmentioning

confidence: 99%

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Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

et al. 2017

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CO conversion covers a wide range of possible application areas from fuels to bulk and commodity chemicals and even to specialty products with biological activity such as pharmaceuticals. In the present review, we discuss selected examples in these areas in a combined analysis of the state-of-the-art of synthetic methodologies and processes with their life cycle assessment. Thereby, we attempted to assess the potential to reduce the environmental footprint in these application fields relative to the current petrochemical value chain. This analysis and discussion differs significantly from a viewpoint on CO utilization as a measure for global CO mitigation. Whereas the latter focuses on reducing the end-of-pipe problem "CO emissions" from todays' industries, the approach taken here tries to identify opportunities by exploiting a novel feedstock that avoids the utilization of fossil resource in transition toward more sustainable future production. Thus, the motivation to develop CO-based chemistry does not depend primarily on the absolute amount of CO emissions that can be remediated by a single technology. Rather, CO-based chemistry is stimulated by the significance of the relative improvement in carbon balance and other critical factors defining the environmental impact of chemical production in all relevant sectors in accord with the principles of green chemistry.

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Section: Carbon Dioxide As a Building Block For Chemical Structuresmentioning

confidence: 99%

Section: Organic Carbonatesmentioning

confidence: 99%

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

et al. 2017

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“…Besides that, we evaluated the meta-hybrid GGA M062X, 52 which was employed in previous computational studies on this reaction. 28 These DFT methods were employed to optimize the geometries and to compute the vibrational frequencies of the alkoxytin compounds Me 2 Sn(OMe) 2 and n Bu 2 Sn(O i Pr) 2 . The calculations using the def2-TZVP basis set required a higher computational cost when compared with the def2-SVP basis set.…”

Section: ■ Computational Detailsmentioning

confidence: 99%

“…Then, 2 can be transformed into the tetranuclear species 3 with high stability, overcoming the energy disadvantage of the thermolysis step (step iii). 27 De Souto et al 28 employed the DFT M06-2X/6-31G(d)-LANL2DZ(Sn) method to evaluate the influence of the substituents in [R 2 Sn(OR)] 2 (R = Me, Ph) on the energy profile of the same reaction. Phenyl substituents in the Sn catalyst lead to smaller energy barriers, a consequence of the influence of this group on the electrophilicity of the Sn atom.…”

Section: ■ Introductionmentioning

confidence: 99%

“…These substituents present the highest barriers for CO 2 insertion, with free energy activation increasing when decreasing the electronegativity of the halogen atom. 28 Beyond the dimer pathway, Kalhor et al 33 made DFT calculations starting from the monomeric species Me 2 Sn-(OMe) 2 . Using the gradient-corrected exchange−correlation PBE functional and the TZP basis set, they evaluated the dimerization of stannanes and the effect of methanol on the catalyst regeneration in different temperatures.…”

Section: ■ Introductionmentioning

confidence: 99%

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Formation of Dimethyl Carbonate from CO₂ and Methanol Catalyzed by Me₂SnO: A Density Functional Theory Approach

2021

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The conversion of CO2 into dimethyl carbonate (DMC) is an environmental and industrial appealing topic because it contributes to reduce the emissions of CO2 and to increase its use as raw material. In the present study we employed the CAM-B3LYP/def2-SVP DFT approach to evaluate the thermodynamic and kinetic parameters for the catalytic conversion of CO2 and methanol into DMC. Starting with the activation of four methanol molecules by the [Me2SnO]2 dimer, we computed all the stationary points along the pathway to convert CO2 and methanol into the DMC. The capture of two CO2 molecules is promoted by an alkoxitin intermediate, in an exothermic process, with low activation energy. Formation of a first DMC occurs after an intramolecular rerrangement involving a tetrahedral intermediate. The formation of a second DMC may occur either in a process similar to the first one or by dimerization of the hemicarbonate formed after releasing the first DMC. In this pathway, the [Me2(OH)SnO(OMe)SnMe2]2 complex is formed. This complex is less reactive than [Me2Sn(OMe)2]2 but still conserves the catalytic activity. Identification of this mechanism suggests that the catalytic action of Me2SnO can be improved by modulating the formation of the final [Me2(OH)SnO(OMe)SnMe2]2 complex.

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High-pressure NMR spectroscopy: An in situ tool to study tin-catalyzed synthesis of organic carbonates from carbon dioxide and alcohols. Part 2 [1]

Laurenczy

Dalebrook

Picquet

et al. 2015

Journal of Organometallic Chemistry

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A DFT Study of the Conversion of CO₂in Dimethylcarbonate Catalyzed by Sn(IV) Alkoxides

Cited by 3 publications

References 1 publication

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

Formation of Dimethyl Carbonate from CO₂ and Methanol Catalyzed by Me₂SnO: A Density Functional Theory Approach

High-pressure NMR spectroscopy: An in situ tool to study tin-catalyzed synthesis of organic carbonates from carbon dioxide and alcohols. Part 2 [1]

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A DFT Study of the Conversion of CO2in Dimethylcarbonate Catalyzed by Sn(IV) Alkoxides

Cited by 3 publications

References 1 publication

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

Formation of Dimethyl Carbonate from CO2 and Methanol Catalyzed by Me2SnO: A Density Functional Theory Approach

High-pressure NMR spectroscopy: An in situ tool to study tin-catalyzed synthesis of organic carbonates from carbon dioxide and alcohols. Part 2 [1]

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A DFT Study of the Conversion of CO₂in Dimethylcarbonate Catalyzed by Sn(IV) Alkoxides

Formation of Dimethyl Carbonate from CO₂ and Methanol Catalyzed by Me₂SnO: A Density Functional Theory Approach