Phenalenyl Based Aluminum Compound for Catalytic C–H Arylation of Arene and Heteroarenes at Room Temperature

Abstract

Main group metal based catalysis has been considered to be a cost-effective alternative way to the transition metal based catalysis, due to the high abundance of main group metals in the Earth’s crust. Among the main group metals, aluminum is the most abundant (7–8%) in the Earth’s crust, making the development of aluminum based catalysts very attractive. So far, aluminum based compounds have been popularly used as Lewis acids in a variety of organic reactions, but chemical transformation demanding a redox based process has never utilized an Al(III) complex as a catalyst. Herein, we tuned the redox noninnocence behavior of a phenalenyl ligand by coupling with Al(III) ion, which subsequently can store the electron upon reduction with K to carry out direct C–H arylation of heteroarenes/mesitylene at ambient temperature. A mechanistic investigation revealed that a three-electron reduced phenalenyl based triradical aluminum(III) complex plays the key role in such catalysis. The electronic structure of the catalytically active triradical species has been probed using EPR spectroscopy, magnetic susceptibility measurements, and electronic structure calculations using a DFT method.