Synthesis, structure and reactivity of SalanH₂-Metal complexes

The present work is an exploration into synthesis of complexes of general formula LH₂M (where M = Mn, Fe, Cu, and Al). The results obtained for L = Salophan (M = Fe (1), Cu (2)); Salomphan (M = Mn (3), Fe(4), Cu(5); Salpan (M = Fe(6), Cu(7)) and L = Salean (M = AlCl) (8) are reported. When 8 is dissolved in MeOH, [SaleanH₂ AlOMe]₂ (9) is formed. In MeOH, and in the presence of air, 1 and 4 undergo oxidation of both the ligand and metal (Fe(II) to Fe(III) to form the "half" Schiff base complexes, [SalophanHFeOMe]₂ (10) and [SalomphanHFeOMe]₂ (11). Compounds 9-11 were structurally characterized. Crystal Data: (9) C₃₆H₄₆Al₂N₄O₇, Space Group P-I (no. 2) with a = 7.536(1) Å, b = 10.513(2) Å, c = 11.997(2) Å, α = 97.72(1), β = 94.040(10)°, γ = 102.73(1), V = 914.8(3) ų and Z = 2. With 226 parameters refined on 1226 reflections having F>6.0σ(F), the final R values were R = 0.0540 and R_w = 0.0565; (10), C₄₆H₄₆Fe₂N₄O₈, Space Group P-1 (no. 2) with a = 9.400(2) Å, b = 10.718(4) Å, c = 12.354(3) Å, α = 76.28(3), β = 67.89(2)°, γ = 86.63(3), V = 1119.7(7) ų and Z = 2. With 289 parameters refined on 1327 reflections having F>6.0a(F), the final R values were R = 0.0672 and R_w = 0.0749; (11), C₄₈H₅₄Fe₂N₄O₈, Space Group P-1 (no. 2) with a = 9.047(2) Å, b= 11.723(2) Å, c= 12.419(3) Å, α = 80.14(2), β = 68.68(3)°, γ = 85.88(2), V = 1208.8(4) ų and Z - 2. With 307 parameters refined on 2171 reflections having F>4.0σ(F), the final R values were R = 0.0546 and R_w = 0.0573.