Chemistry of Diphenylphosphine Adducts of Tris(Neopentyl)- and Tris(Trimethylsilylmethyl)-Gallium and -Indium Including the Crystal and Molecular Structure of (Me3CCH2)3Ga.P(H)Ph2

摘要

The adducts (Me3CCH2)3Ga.P(H)Ph2 and (Me3SiCH2)3Ga.P(H)Ph2 have been prepared as crystalline solids at room temperature and characterized by cryoscopic molecular weight measurements in benzene solution and 1H NMR, 31P NMR and IR spectroscopic data. The molecular weight studies demonstrate that both adducts are extensively dissociated in solution and that Ga(CH2CMe3)3 is a stronger Lewis acid than Ga(CH2SiMe3). An X-ray structural study defined the nature of (Me3CCH)23Ga.P(H)Ph2 in the solid state. The colorless crystal contains two discrete molecules in each unit cell. The compound crystallizes in the triclinic space group P1. The adduct has a relatively long G-P distance fo 2.683(5)A and the alpha-carbon atoms of the substituents on gallium and phosphorus are essentially but not perfectly eclipsed. The syntheses of (Me3CCH2)3In.P(H)Ph2 and (Me3SiCH2)3In.P(H)Ph2 were attempted but room temperature elimination reactions, which produced CMe4 and SiMe4, respectively, and the appropriate organoindium phosphides, precluded and isolation of adducts. (AW)