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

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.