4.5 Article

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

Journal

ORGANOMETALLICS
Volume 32, Issue 23, Pages 7186-7194

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/om400876j

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Funding

  1. PAPIIT-DGAPA-UNAM [IN-210613]
  2. CONACYT [0178265]

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The reaction of CO, with Et3SiH catalyzed by the nickel complex [(dippe)Ni(mu-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 (85-89%), at 80 degrees C for 1 h. Further reactivity of the silyl formate to yield formic acid, formamides, and alkyl formates was also investigated.

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