固体表面における協奏的触媒作用：金属錯体・金属カチオン・有機分子の集積による有機反応の促進

Abstract

Bifunctional catalytic surface enables significant acceleration of organic reactions by concerted catalysis. For example, allylation of nucleophiles smoothly occurred on a SiO2 surface possessing both Pd complex and tertiary amine. In the case of the catalysts with Pd-bisphosphine complex and 1,4-diazabicyclo [2.2.2] octane (DABCO) on same SiO2 surface, the turnover number (TON) value based on Pd species approached up to 106000. Other reaction systems containing Rh complex and In cation for 1,4-addition of organoboronic acid and cyanation reaction of aldehyde, respectively, are also described. These SiO2- and SiO2-Al2O3-supported catalysts were characterized by several spectroscopic techniques, such as solid-state NMR, X-ray absorption fine structure (XAFS) spectroscopy, and X-ray photoelectron spectroscopy (XPS), for atomic or molecular-level understanding. Reaction mechanisms including acceleration process is also discussed based on several experiments.