Nickel-Catalyzed Hydrosilylation of CO2 in the Presence of Et3B for the Synthesis of Formic Acid and Related Formates

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• 作者：Lucero Gonz谩lez-Sebasti谩n ; Marcos Flores-Alamo ; Juventino J. Garcı ; ́ ; a
• 刊名：Organometallics
• 出版年：2013
• 出版时间：December 9, 2013
• 年：2013
• 卷：32
• 期：23
• 页码：7186-7194
• 全文大小：429K
• 年卷期：v.32,no.23(December 9, 2013)
• ISSN：1520-6041

文摘

The reaction of CO₂ with Et₃SiH catalyzed by the nickel complex [(dippe)Ni(渭-H)]₂ (1) afforded the reduction products Et₃SiOCH₂OSiEt₃ (12%), Et₃SiOCH₃ (3%), and CO, which were characterized by standard spectroscopic methods. Part of the generated CO was found as the complex [(dippe)Ni(CO)]₂ (2), which was characterized by single-crystal X-ray diffraction. When the same reaction was carried out in the presence of a Lewis acid, such as Et₃B, the hydrosilylation of CO₂ efficiently proceeded to give the silyl formate (Et₃SiOC(O)H) in high yields (85鈥?9%), at 80 掳C for 1 h. Further reactivity of the silyl formate to yield formic acid, formamides, and alkyl formates was also investigated.