Journal of the American Chemical Society, Vol.132, No.31, 10660-10661, 2010
Tandem Frustrated Lewis Pair/Tris(pentafluorophenyl)borane-Catalyzed Deoxygenative Hydrosilylation of Carbon Dioxide
The frustrated Lewis pair system consisting of 2 equiv of 2,2,6,6-tetramethylpiperidine (TMP) and tris(pentafluorophenyl)borane [B(C6F5)(3)] activates carbon dioxide to form a boratocarbamate-TMPH ion pair. In the presence of triethylsilane, this species is converted to a silyl carbamate and the known ion pair [TMPH](+)[HB(C6F5)(3)(-), which recently was shown to react with CO2 via transfer of the hydride from the hydridoborate to form the formatoborate [TMPH](+)[HC(O)-OB(C6F5)3](-). In the presence of extra B(C6F5)(3) (0.1-1.0 equiv) and excess triethylsilane, the formatoborate is rapidly hydrosilated to form a formatosilane and regenerate [TMPH](+)[HB(C6F5)3](-). The formatosilane in turn is rapidly hydrosilated by the B(C6F5)(3)/Et3SiH system to CH4, with (Et3Si)(2)O as the byproduct. At low [Et3SiH], intermediate CO2 reduction products are observed; addition of more CO2/Et3SiH results in resumed hydrosilylation, indicating that this is a robust, living tandem catalytic system for the deoxygenative reduction of CO2 to CH4.