Siemens Reloaded: Chloride‐Assisted Selective Hydrodechlorination of SiCl 4 to HSiCl 3

Trichlorosilane is the key intermediate for the large‐scale production of polycrystalline silicon in the Siemens and Union Carbide processes. Both processes, however, are highly inefficient, and over two thirds of the trichlorosilane employed is converted to unwanted silicon tetrachloride accumulating in millions of tons per year on a global scale. In this combined experimental and theoretical study we report an energetically and environmentally benign synthetic protocol for the highly selective conversion of SiCl 4 to HSiCl 3 using organohydridosilanes as recyclable hydrogen transfer reagents in combination with onium chlorides as efficient catalysts. We put the same protocol to further use demonstrating the quantitative conversion of higher oligosilane residues, which form as another unwanted and potentially hazardous byproduct of Siemens processes, to HSiCl 3 in a low‐temperature recycling step.