文摘
The selective scission of chemical bonds is always of great significance in organic chemistry. The cleavage of strong carbon鈥揷arbon 蟽 bonds in the unstrained systems remains challenging. Here, we report the selective hydrogenolysis of carbon鈥揷arbon 蟽 bonds in primary aliphatic alcohols catalyzed by supported metals under relatively mild conditions. In the case of 1-hexadecanol hydrogenolysis over Ru/TiO2 as a model reaction system, the selective scission of carbon鈥揷arbon bonds over carbon鈥搊xygen bonds is observed, resulting in n-pentadecane as the dominant product with a small quantity of n-hexadecane. Theoretical calculations reveal that the 1-hexadecanol hydrogenolysis on flat Ru (0001) undergoes two parallel pathways: i.e. carbon鈥揷arbon bond scission to produce n-pentadecane and carbon鈥搊xygen bond scission to produce n-hexadecane. The removal of adsorbed CO on a flat Ru (0001) surface is a crucial step for the 1-hexadecanol hydrogenolysis. It contributes to the largest energy barrier in n-pentadecane production and also retards the rate for n-hexadecane production by covering the active Ru (0001) surface. The knowledge presented in this work has significance not just for a fundamental understanding of strong carbon鈥揷arbon 蟽 bond scission but also for practical biomass conversion to fuels and chemical feedstocks.