Synthesis of substituted β-diketiminate gallium hydrides via oxidative addition of H–O bonds

Abstract

Oxidative addition of LGa into the OH bonds from HCCCH₂OH, Ph₂Si(OH)₂, (nBuO)₂P(O)(OH) and 4-MeC₆H₄S(O)₂(OH) results in the formation of four compounds of the general formula LGa(H)(O–X). The correlation of the Ga–O bond length and the strength of the Ga–H bond depending on the acidity of the OH group in the starting materials has been demonstrated. The molecular structures of all four compounds have been determined using single crystal X-ray diffraction experiments. DFT calculations were performed on the reacting complex of LGa with propargyl alcohol and show an OH⋯Ga hydrogen bond as the first interaction between the reagents. This reacting complex changes into a D–A complex where the oxygen atom of the propargyl alcohol coordinates to the gallium atom and in a concerted reaction the oxidative addition product is formed.