GROUP-13 AZATRANES - STRUCTURE AND REACTIVITY

The new monomeric azagallatranes ga(RNCH(2)CH(2))(3)N (R = SiMe(3), 10 ; SiMe(2)-t-Bu, 11) and dimeric azagallatrane [Ga(MeNCH(2)CH(2))(3)N]( 2), 14, were prepared by two synthetic routes: (i) the transamination reaction of [Ga (NMe(2))(3)](2), with (MeNHCH(2)CH(2))(3)N, 2, and (ii ) the transmetalation reaction of [Al(MeNCH(2)CH(2))(3)N](2), 12, with Ga(acac)(3) (acac = penta-2,5-dienoate). Dimeric azaalumatrane 12, mo nomeric azaalumatranes Al(RNCH(2) CH2)(3)N (R = SiMe(3), 8; SiMe(2)-t- Bu, 9), and azaboratrane B(MeNCH(2)CH(2))(3)N, 6, react with a variety of alkoxides giving transition metal or main-group element azatranes. The molecular structures of 12 and 14 were established by X-ray diffr action experiments, and both possess an unusual cis configuration of t he substituents on the central four-membered (M-N)(2) ring. Crystal da ta: 12, a = 37.372(10) Angstrom, b = 14.379(2) Angstrom c = 8.774(2) A ngstrom, V = 4714.9(1) Angstrom(3), Z = 8, orthorhombic space group Pb ca, R = 5.0%; 14, a = 9.716(1) Angstrom, b = 11.325(2) Angstrom, c = 1 1.343(1) Angstrom, alpha = 110.36(2)degrees, beta = 97.87(1)degrees, g amma = 90.34(1)degrees, V = 1157.2(3) Angstrom(3), Z = 2, triclinic sp ace group P $$($) over bar 1, R = 4.7%.