CHARACTERIZATION OF GALLIUM-NITROGEN ADDUCTS BY X-RAY STRUCTURAL AND NMR SPECTRAL STUDIES. CRYSTAL STRUCTURE OF [(PhMe2CCH2)2GaCI]2 AND OF ITS MONOMERIC t-BUTYLAMINE ADDUCT, (PhMe2CCH2)2GaCI[NH2(t-Bu)]

Abstract The nature of [(PhMe2CCH2)2GaCl]2 and its adducts with NH2(t-Bu) and NH2(n-Pr) have been investigated. [(PhMe2CCH2)2GaCl]2 crystallizes in the monoclinic space group P21/c with a=11.2495(16)A, b = 21.4977(32)A, c = 7.8337(15)A, β = 93.489(14)°, V= 1891.0(5)A3 and D(calcd.)= 1.305 Mg/m3 for Z = 2. The structure was refined to R(F) = 4.2% for 1672 reflections above 6[sgrave](F). The molecule has perfect Ci symmetry, a planar Ga(μ-Cl)2Ga core and an expanded C(α)-Ga-C(α) angle of 137.9(3)° between the neophyl ligands. (PhMe2CCH2)2-GaCl[NH2(t-Bu)] crystallizes in the monoclinic space group P21/n with a = 6.4023(10) A, b= 17.4274(25) A, c = 22.2389(38) A, β = 94.939(13)°, V= 2472.2(7)A3 and D(calcd.) = 1.225 Mg/m3 for Z = 4. This structure was refined to R(F) = 3.9% for 1700 reflections above 6[sgrave](F). The crystal structure is stabilized by intermolecular Cl … H-N hydrogen bonds and the central Ga(III) atom has a distorted tetrahedral geometry. A benzene solution of (PhMe2-CCH2)2GaCl[NH2(t-Bu)] is...