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

文献情報

出版日 2010-11-22

DOI 10.1039/C0CP02089C

インパクトファクター 3.676

著者

Mahboubeh Poor Kalhor, Henry Chermette, Stéphane Chambrey, Danielle Ballivet-Tkatchenko

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要旨

The formation of dimethyl carbonate (DMC) from CO2 and methanol with the dimer [n-Bu2Sn(OCH3)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, CO2/toluene, supercritical CO2, and CO2/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 [(CH3)2Sn(OCH3)2]2/CO2 system show that the exothermic insertion of CO2 into the Sn–OCH3 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–OCH3 bonds are prompt to insert CO2. These results provide new insight into the reaction mechanism and catalyst design to enhance the turnover numbers.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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

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