BH3 Activation by Phosphorus-Stabilized Geminal Dianions: Synthesis of Ambiphilic Organoborane, DFT Studies, and Catalytic CO2 Reduction into Methanol Derivatives

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• 作者：Mathieu Lafage ; Anthony Pujol ; Nathalie Saffon-Merceron ; Nicolas Mézailles
• 刊名：ACS Catalysis
• 出版年：2016
• 出版时间：May 6, 2016
• 年：2016
• 卷：6
• 期：5
• 页码：3030-3035
• 全文大小：402K
• 年卷期：0
• ISSN：2155-5435

文摘

The reaction of the geminal dianion (SCS)^2– 1 with 2 equiv of BH₃·SMe₂ leads to the isolation and full characterization of the new organoborane [(SCS)BH₂][Li(THF)₂] 2, in which the C═B bond possesses ambiphilic, multiple character. Treatment of 2 with another 1 equiv of BH₃·SMe₂ allows the isolation of the rare cyclic diborane species [(SCS)B₂H₅][Li(OEt₂)] 4. The electronic structures of both compounds were investigated by means of DFT calculations. Compound 4 is an efficient catalyst for the reduction of CO₂ to methanol derivatives by BH₃·SMe₂. A TON of ca. 2800 (TOF = 127 h^–1) was achieved using 0.1 mol % of 4 in THF.