LOW OXIDATION-STATE GALLIUM COMPOUNDS - SYNTHESIS AND CHARACTERIZATION OF [GA(CH2CME3)]N

The new organogallium(I) compound [Ga(CH2CMe3)]n has been prepared by the reduction of Ga(CH2CMes)2CI by using either sodium or lithium with naphthalene in THF. When the reagents were combined at -78-degrees-C, a yellow intermediate, a neopentylgallium(III) derivative of dihydronaphthalene C10H8[Ga(CH2CMe3)2]2.2MCl (M = Li, Na) was formed. Warming of the solution to 0-25-degrees-C resulted in decomposition of the yellow intermediate and formation of a reddish brown solution of [Ga(CH2CMe3)]n, Ga(CH2CMe3)3, C10H8, and either NaCl or LiCl. The gallium(I) product was a vitreous solid and was characterized by complete elemental analyses, hydrolyses with HCl/H2O and with DCl/D2O, oxidation with HgCl2 and with I2, cryoscopic molecular weight studies in benzene solution, and IR and NMR spectroscopic studies. All data support the conclusion that [Ga(CH2CMe3)]n exists as a mixture of species which are gallium cages. The numbers of gallium atoms in these cages might range from 6 to 12 atoms.