Synthesis, Crystal Structures, and Catalytic Oxidation of Olefins of Novel Oxomolybdenum(VI) Clusters

Resumo

Two Mo(VI) clusters, (H₂L)₃[Mo₇O₁₂(μ₂-O)₈(μ₃-O)₄] · 3H₂O (I) and (H₂L)₂[Mo₈O₁₄(μ₂-O)₆(μ₃-O)₄(μ₅-O)₂] · 4DMF (II), derived from MoO₂(Acac)₂ and N-methylethane-1,2-diamine (L) in water and DMF, respectively, are reported. The complexes were characterized by single crystal structure analysis (CIF files CCDC nos. 1846032 (I) and 1443681 (II)). Compound I contains a seven nuclear molybdenum(VI) complex anion, three H₂L cations and three water molecules. Compound II contains an eight nuclear molybdenum(VI) complex anion, two H₂L cations and four DMF molecules. All Mo atoms are in octahedral coordination. Complex I crystallized as monoclinic space group P2₁/n with unit cell dimensions a = 12.3005(12), b = 17.3944(17), c = 15.9446(16) Å, β = 93.862(2)°, V = 3403.8(6) ų, Z = 4, R₁ = 0.0795, wR₂ = 0.1677. Complex II crystallized as monoclinic space group P2₁/n with unit cell dimensions a = 11.1465(13), b = 16.460(2), c = 12.7942(16), β = 97.368(2)°, V = 2328.0(5) ų, Z = 2, R₁ = 0.0362, wR₂ = 0.0754. The complexes were tested as catalyst for the oxidation of olefins and showed effective activity.