Experimental and Theoretical Studies on the Reduction of CO2 to CO with Chloro(methyl) disilane Components from the Direct Process

Three disilanes, (CH3)(3)SiSi(CH3)(3), Cl(CH3)(2)SiSi(CH3)(2)Cl, and Cl-2(CH3) SiSi(CH3) Cl-2, all representing components of the Direct Process residue for the industrial synthesis of chloromethylsilanes, were evaluated for their abilities to reduce carbon dioxide to carbon monoxide upon treatment with fluoride salts. In particular, Cl(CH3)(2)SiSi(CH3)(2)Cl proved to be highly efficient upon the use of stoichiometric amounts of potassium bifluoride. DFT calculations performed on the reduction steps with (CH3)(3)SiSi(CH3)(3) and fluorinated analogues of this disilane suggest that the previously proposed pathway involving an intermediate silacarboxylic acid is plausible.