DFT Study on Activation of Carbon Dioxide by Dimethyltin Dimethoxide for Synthesis of Dimethyltin Carbonate

Miyake, Nobuhisa; Nagahara, Hajime; Bijanto, Budianto; Wakamatsu, Kan; Orita, Akihiro; Otera, Junzo

doi:10.1021/om100484r

Cited by 7 publications

(16 citation statements)

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“…The evaluation of Sn-O bond association with dimethyldimethoxystannane and related distannoxane as well as the role of monomeric di-n-butyltin diacetate in polyurethane synthesis have been reported recently. 14,15 Whilst our work was in progress, Miyake et al 16 published a DFT study on the activation of CO 2 by dimethyldimethoxystannane for the synthesis of DMC. The strong association of the Sn-O bond is the driving force for the facile reaction.…”

Section: Introductionmentioning

confidence: 99%

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From CO2 to dimethyl carbonate with dialkyldimethoxystannanes: the key role of monomeric species

Kalhor

Chermette

Chambrey

et al. 2011

Phys. Chem. Chem. Phys.

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The formation of dimethyl carbonate (DMC) from CO(2) and methanol with the dimer [n-Bu(2)Sn(OCH(3))(2)](2) was investigated by experimental kinetics in support of DFT calculations. Under the reaction conditions (357-423 K, 10-20 MPa), identical initial rates are observed with three different reacting mixtures, CO(2)/toluene, supercritical CO(2), and CO(2)/methanol, and are consistent with the formation of monomeric di-n-butyltin(iv) species. An intramolecular mechanism is, therefore, proposed with an Arrhenius activation energy amounting to 104 ± 10 kJ mol(-1) for DMC synthesis. DFT calculations on the [(CH(3))(2)Sn(OCH(3))(2)](2)/CO(2) system show that the exothermic insertion of CO(2) into the Sn-OCH(3) bond occurs by a concerted Lewis acid-base interaction involving the tin center and the oxygen atom of the methoxy ligand. The Gibbs energy diagrams highlight that, under the reaction conditions, the dimer-monomer equilibrium is significantly shifted towards monomeric species, in agreement with the experimental kinetics. Importantly, the two Sn-OCH(3) bonds are prompt to insert CO(2). These results provide new insight into the reaction mechanism and catalyst design to enhance the turnover numbers.

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Section: Introductionmentioning

confidence: 99%

“…Finally, the calculated free Gibbs energies are fully compatible with such a mechanism, and the corresponding diagrams are compared to that of the literature. 16…”

Section: Introductionmentioning

confidence: 99%

From CO2 to dimethyl carbonate with dialkyldimethoxystannanes: the key role of monomeric species

Kalhor

Chermette

Chambrey

et al. 2011

Phys. Chem. Chem. Phys.

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“…First, the synthesis of bis(2,2,2-trifluoroethyl) carbonate (1)w as attempted by dehydration condensation (methodI). Various dehydrating agents have been reported to be applicable to the synthesis of DACs from CO 2 and alcohols, [22] so we employed two of them for the dehydration condensation of TFEA and CO 2 .U pon using 2-cyanopyridine [22c,d] as ad ehydrating agent, the desired reaction hardly proceeded (seet he Supporting Information). This wasp robablyb ecause of the lower nucleophilicity of TFEA compared with that of nonfluorinated alkyl alcohol.…”

Section: Methods I: Dehydration Condensationmentioning

confidence: 99%

“…Aiming at the synthesis of fluorinated DAC 1,w ee xamined three methods I-III referring to the previously reported methods fort he synthesis of DACs from CO 2 ,a ss hown in Scheme 1a: [17a, 19] I) dehydrative condensation of CO 2 and two mol- ecules of alcohol; [22] II) three-component coupling of alcohol, CO 2 ,a nd electrophile; [23] and III) dialkylationo fi norganic carbonatebye lectrophile. [24] The above three methods are classified by the method for introduction of the two alkyl groups into the target molecules (Scheme 1b).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Fluorinated Dialkyl Carbonates from Carbon Dioxide as a Carbonyl Source

et al. 2020

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Fluorinated dialkyl carbonates (DACs), which serve as environmentally benign phosgene substitutes, were produced successfully from carbon dioxide either directly or indirectly. Nucleophilic addition of 2,2,2‐trifluoroethanol to carbon dioxide and subsequent reaction with 2,2,2‐trifluoroethyltriflate (3 a) afforded bis(2,2,2‐trifluoroethyl) carbonate (1) in up to 79 % yield. Additionally, carbonate 1 was obtained through the stoichiometric reaction of 3 a and cesium carbonate. Although bis(1,1,1,3,3,3‐hexafluoro‐2‐propyl) carbonate (4) was difficult to obtain by either of the above two methods, it could be synthesized through the transesterification of carbonate 1.

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“…Theoretical studies on the absorption, catalysis, and activation of the CO 2 molecule have been reported [9][10][11][12][13][14][15][16][17][18]. In the present paper, I provide a systematic theoretical study of the bonding features, hyperconjugation, and electronic structures of a series of transition metal CO 2 complexes with various coordination models.…”

Section: Introductionmentioning

confidence: 94%

Quantum chemical studies on a series of transition metal carbon dioxide complexes: Metal–carbon bonding and electronic structures

Liu

2012

Molecular Physics

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DFT Study on Activation of Carbon Dioxide by Dimethyltin Dimethoxide for Synthesis of Dimethyltin Carbonate

Cited by 7 publications

References 0 publications

From CO2 to dimethyl carbonate with dialkyldimethoxystannanes: the key role of monomeric species

From CO2 to dimethyl carbonate with dialkyldimethoxystannanes: the key role of monomeric species

Synthesis of Fluorinated Dialkyl Carbonates from Carbon Dioxide as a Carbonyl Source

Quantum chemical studies on a series of transition metal carbon dioxide complexes: Metal–carbon bonding and electronic structures

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