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 β-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 LLi·OEt2 with MeMCl2 affords LM(Me)Cl (M = Al (1), Ga (2), In (3)) and LGaBr2
(4) with GaBr3. Reduction of LGa(Me)Cl with LiH·BEt3 leads to the formation of LGa(Me)H (10). Synthesis of
LGaH2 (12) has been accomplished by reacting LGaI2 (8) with LiH·BEt3. 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 LAl(Me)Cl with
Me3SnF while the latter was isolated in a reaction of LAlH2 with BF3·OEt2. Similarly reaction of LGaI2 (8) with
Me3SnF affords LGaF2 (9). Compounds reported herein have been characterized by elemental analyses, IR, NMR,
EI-MS, and single-crystal X-ray diffraction techniques.