Syntheses, characterization, and X-ray crystal structures of β-diketiminate group 13 hydrides, chlorides, and fluorides

A series of organometallic compounds of group 13 metals supported by the sterically encumbered beta-diketiminate ligand containing hydrides, fluorides, chlorides, and bromide have been synthesized and structurally characterized. The synthetic strategy applied utilizes halide metathesis and reduction of metal chlorides to the corresponding hydrides. Thus, the reaction of (LLiOEt2)-O-. with MeMCl2 affords LM(Me)Cl (M = Al (1), Ga (2), In (3)) and LGaBr2 (4) with GaBr3. Reduction of LGa(Me)Cl with (LiHBEt3)-B-. leads to the formation of LGa(Me)H (10). Synthesis of LGaH2 (12) has been accomplished by reacting LGal(2) (8) with (LiHBEt3)-B-.. LAl(Me)Cl (1) and LAlH2 (6) have been converted to LAl(Me)F (5) and LAlF2 (7), respectively. The former was obtained in a reaction of LAI(Me)Cl with Me3SnF while the latter was isolated in a reaction of LAlH2 with (BF3OEt2)-O-.. Similarly reaction of LGal(2) (8) with Me3SnF affords LGaF2 (9). Compounds reported herein have been characterized by elemental analyses, IR, NMR, El-MS, and single-crystal X-ray diffraction techniques.