Steven J. Schauer

Aminoalane dimers and trimers. An examination of structural and steric trends

Abstract Reaction of aluminum alkyls with primary or secondary amines readily affords dimeric or trimeric aminoalanes. Steric constraints of the substituents on aluminum and nitrogen substantially affect the structural nature of the products. Ring size, conformational data, and structural trends are reported for a number of dimeric and trimeric aminoalanes.

THIA AND AZA BASED ALANES: SYNTHESIS AND MOLECULAR STRUCTURE OF [Np2Al-N(H)Ph]2, [Np2Al-SNp]2, AND [Ph2Al-N(H)Ph′]2 (Np = Me3CCH2-; Ph = Biphenyl)

Abstract Reaction of trineopentylaluminum, Np3Al (Np = Me3CCH2-), with 1,2-diphenylhydrazine, Ph(H)N-N(H)Ph, or elemental sulfur in toluene affords the dimeric crystalline products [Np2Al-N(H)Ph]2, I, and [Np2Al-SNp]2, II, respectively. The etherate of triphenylalumium, Ph3Al·OEt2, when allowed to react with 2-aminobiphenyl, yields the dimer [Ph2AL-N(H[Ph′]2, (Ph′ = Biphenyl) III. Each compound has been characterized by 1H NMR, elemental analysis, and single crystal X-ray diffraction. I and II crystallize in the monoclinic space group P21/n (No. 14); I: a = 9.801 (3), b = 20.490 (9), c = 17.569 (8) A, β = 97.81 (3)°, V = 3496 (3) A3 for Z = 4; II: a = 10.191 (5) A, b = 10.907 (5) A, c = 16.779 (6) A, β = 97.18 (3)°, V = 1851 (1) A8 for Z = 2. Refinement of I converged at R = 0.051, R w = 0.049, while refinement of II converged at R = 0.051, R w = 0.066. III crystallizes in the tetragonal space group l41/a (No. 88); a = 26.628 (5) A, c = 11.017 (4) A, V = 7812 (4) A3, for Z = 8. Refinement of III converged...

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

Abstract The sterically demanding Group 13 amide dimers [(i-Bu)2Al-N(H)Mes]2 (I), [(i-Bu)Al-N(H)Ph(t-Bu)2-μ-(CMe2CH2)]2 (II), [Me2In-N(H)Ph′]2 (III), and [(i-Bu)2Al-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)2AIH or Me3In with the respective primary amine and characterized by 1H NMR, elemental analyses, and single crystal X-ray diffraction. I crystallizes in the triclinic space group P1 with unit cell parameters a = 9.272(1), b = 9.718(2), c = 11.585(2)A, α = 101.76(1)°, β = 106.69(1)°, γ = 109.70(1)°, V=887.5(2)A3, and Dcalc = 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 < 2 < 45.0° converged at R = 0.043 and R w = 0.054. II crystallizes in the monoclinic space group P21/c with unit cell parameters a = 11.292(5), b = 17.544(9), c = 11.532(5)A, β = 107.99(4)°, V = 2173(2)A3, and Dcalc = 1.05 g cm−3 for Z = 2. Least-squares refinement based on...