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Conversion of Carbon Dioxide into Methanol with Silanes over N-Heterocyclic Carbene Catalysts

Conversion of Carbon Dioxide into Methanol with Silanes over N-Heterocyclic Carbene Catalysts. Siti Nurhanna Riduan, Yugen Zhang,* and Jackie Y. Ying*. Angew. Chem. Int. Ed . 2009 , 48 , 3322 –3325. TON = 78~400 TOF = 2.8~17 h -1.

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Conversion of Carbon Dioxide into Methanol with Silanes over N-Heterocyclic Carbene Catalysts

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  1. Conversion of Carbon Dioxide into Methanol with Silanes overN-Heterocyclic Carbene Catalysts Siti Nurhanna Riduan, Yugen Zhang,* and Jackie Y. Ying* Angew. Chem. Int. Ed. 2009, 48, 3322 –3325

  2. TON = 78~400 TOF = 2.8~17 h-1 H. Koinuma, F. Kawakami, H. Kato, H. Hirai, J. Chem. Soc. Chem. Commun. 1981, 213. TON = 1840 TOF = 25.5 h-1

  3. Figure 1.13C NMR spectra from the reaction of 13CO2, diphenylsilane and Imes-CO2 catalyst 1 (5 mol%) in [D7]DMF. Proton-decoupled spectra are shown in (a), (b), and (d); the spectrum in (c) was recorded without proton decoupling. The spectra in (a) and (b) show the conversion of 13CO2 (*) to 13CH2(OSiR3)2 (▼) to 13CH3OSiR3 (#). The spectrum in (d) shows that all 13CO2 was converted to 13CH3OSiR3 24 h after additional silane was introduced to the mixture in (b).

  4. nucleophilic carbene would activate CO2 Si-H bond activated by a free carbene This catalytic cycle would continue until the supply of hydrosilane as a hydride donor is exhausted.

  5. DMF, as a Lewis base, will also activate silane and speed up the reaction

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