GROUP 13 AMIDES. SYNTHESES AND MOLECULAR STRUCTURES OF [(i-Bu)2Al-N(H)Mes]2,[(i-Bu)Al-N(H)Ph(t-Bu)2-μ-(CMe2CH2)]2, [Me2In-N(H)Ph′]2, AND [(i-Bu)2Al-N(H)Ada]2

The sterically demanding Group 13 amide dimers [(i-Bu) 2 Al-N(H)Mes] 2 (I), [(i-Bu)Al-N(H)Ph(t-Bu) 2 -μ-(CMe 2 CH 2 )] 2 (II), [Me 2 In-N(H)Ph′] 2 (III), and [(i-Bu) 2 Al-N(H)Ada] 2 (IV) (Ada = adamantyl; Bu=butyl; Mes = Ph(Me) 3 ; Ph = phenyl; Ph′= 2-biphenyl) have been prepared by reaction of (i-Bu) 2 AIH or Me 3 In with the respective primary amine and characterized by 1 H NMR, elemental analyses, and single crystal X-ray diffraction. I crystallizes in the triclinic space group P 1 with unit cell parameters a = 9.272(1), b = 9.718(2), c = 11.585(2)Å, α = 101.76(1)°, β = 106.69(1)°, γ = 109.70(1)°, V=887.5(2)Å 3 , and D calc = 1.03g cm −3 for Z = 1. Least-squares refinement based on 1644 observed reflections with intensities I > 3σ(I) in the range 3.5 < 2θ < 45.0° converged at R = 0.043 and R w = 0.054. II crystallizes in the monoclinic space group P2 1 / c with unit cell parameters a = 11.292(5), b = 17.544(9), c = 11.532(5)Å, β = 107.99(4)°, V = 2173(2)Å 3 , and D calc = 1.05 g cm −3 for Z = 2. Least-squares refinement based on 1819 observed reflections with intensities I > 3σ(I) in the range 3.5 < 2θ < 45.0° converged at R = 0.066 and R w = 0.088. III crystallizes in the triclinic space group P 1 with unit cell parameters a = 9.710(1), b = 17.755(1), c = 9.109(2)Å, α = 102.27(1)°, β = 117.46(2)°, γ = 88.38(1)°, V = 1357(2)Å 3 , and D calc = 1.53 g cm −3 for Z = 2. Least-squares refinement based on 2569 observed reflections with intensities I > 3σ(I) in the range 4.0 < 2θ < 50.0° converged at R = 0.035 and R w = 0.049. These compounds reside in trans conformations about M 2 N 2 (M = Al or In) four-membered rings. II is an interesting metallated product. The 1 H NMR spectrum of IV suggests the presence of both trans and cis isomers (in approximately a 2:1 ratio).