Transition Metal-like Oxidative Addition of C–F and C–O Bonds to an Aluminum(I) Center

Abstract

Oxidative addition of very robust C–F and C–O bonds has been accomplished in reactions of the aluminum(I) compound NacNacAl (1, NacNac = [ArNC(Me)CHC(Me)NAr]− and Ar = 2,6-Pri2C6H3) with fluoroarenes, fluoroalkanes, and ethers. Similar to the transition metals, the ease of aryl C–F oxidative addition decreases as the degree of fluorination diminishes on the aromatic substrate. As well, kinetic studies on the addition of 1,2,3,4-tetrafluorobenzene to compound 1 revealed a second-order reaction characterized by a very negative entropy of activation (ΔS⧧ = −113.6(3) J/K·mol), consistent with a transition metal-like oxidative addition process.