Oxidative Addition of σ Bonds to an Al(I) Center

The Al­(I) compound NacNacAl (1, NacNac = [ArNC­(Me)­CHC­(Me)­NAr]− and Ar = 2,6-Pri2C6H3) reacts with H–X (X = H, Si, B, Al, C, N, P, O) σ bonds of H2, silanes, borane (HBpin, pin = pinacolate), allane (NacNacAlH2), phosphine (HPPh2), amines, alcohol (PriOH), and Cp*H (Cp* = pentamethylcyclopentadiene) to give a series of hydride derivatives of the four-coordinate aluminum NacNacAlH­(X), which are characterized herein by spectroscopic methods (NMR and IR) and X-ray diffraction. This method allows for the syntheses of the first boryl hydride of aluminum and novel silyl hydride and phosphido hydride derivatives. In the case of the addition of NacNacAlH2, the reaction is reversible, proving the possibility of reductive elimination from the species NacNacAlH­(X).