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Mechanistic Insights into the Reduction of Carbon Dioxide with Silanes over NHeterocyclic Carbene Catalysts
| Content Provider | Semantic Scholar |
|---|---|
| Author | Riduan, Siti Nurhanna Ying, Jackie Y. Zhang, Yunwu |
| Copyright Year | 2013 |
| Abstract | or photochemical means, and CO2 as a comonomer in the synthesis of polycarbonates and as a starting material for the synthesis of motifs commonly found in pharmaceuticals. Since our report of a successful reduction of CO2 to methanol through an organocatalyzed hydrosilylation process, a number of publications have ensued. The use of frustrated Lewis pairs, first mooted by the research groups of Stephan and Erker, has been applied to activate H2 heterolytically, [6] and more recently, frustrated Lewis pairs were shown to reversibly uptake and release CO2. [7] A recent report on the room-temperature reduction of CO2 to methanol with a frustrated Lewis pair of aluminum and phosphines with ammonia borane as a hydride donor yielded up to 51 % methanol, as determined by NMR spectroscopy. The same reduction with four equivalents of tetramethylpiperidine–boron-based frustrated Lewis pairs in an atmosphere of H2 resulted in quantitative conversion with methanol isolated in 25 % yield. The same tetramethylpiperidine–boron-based frustrated Lewis pair system was used in combination with triethylsilane as a reductant to yield methane. The reduction of CO2 catalyzed by transition-metal complexes is still widely studied, with a recent report on an efficient nickel catalyst for the reduction of CO2, with boron as a sacrificial reductant. These recent reports illustrate that the catalytic reduction of CO2 to methanol remains a research area of considerable interest, as it may be a viable alternative for the industrial synthesis of methanol from CO2. Although such reactions are still in the research stage, it is important to understand their underlying mechanisms, so as to bring about major advances in this field. Recently, Wang's group reported a detailed computational mechanistic study on the N-heterocyclic carbene (NHC) catalyzed CO2 reduction to methanol with hydrosilane that we reported in 2009. However, we have found that their calculated mechanism was partially inconsistent with our experimental results. Herein, we report new insights into the hydrosilylation of CO2 with NHCs by combining experiments with DFT calculations. |
| File Format | PDF HTM / HTML |
| Alternate Webpage(s) | https://oar.a-star.edu.sg/jspui/bitstream/123456789/3521/1/chemcatchem.pdf |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
