A dinuclear oxo-bridged molybdenum(VI) complex containing a bidentate pyrazolylpyridine ligand: Structure, characterization and catalytic performance for olefin epoxidation

• A dinuclear MoVI complex containing a pyrazolylpyridine ligand (pypzEA) is reported.
• [Mo2O4(μ2-O)Cl2(pypzEA)2] was obtained directly from mononuclear [MoO2Cl2(pypzEA)].
• The crystal and molecular structures of the dinuclear complex are described.
• The oxo-bridged complex was tested in the catalytic epoxidation of cis-cyclooctene.
• The catalytic results compare favorably with those reported for related complexes.

The oxo-bridged dinuclear complex [Mo2O4(μ2-O)Cl2(pypzEA)2] (2) (pypzEA = ethyl[3-(pyridin-2-yl)-1H-pyrazol-1-yl]acetate) was obtained upon the treatment of [MoO2Cl2(pypzEA)] (1) with ethanol. The molecular structure of 2 consists of two highly distorted {MoClN2O3} octahedra sharing a corner oxygen atom, with a MoOMo “kink” angle of 163.2(2)° and a Mo⋯Mo separation of 3.7029(7) Å. Catalytic results with 2 for the epoxidation of cis-cyclooctene using tert-butylhydroperoxide as oxidant compare favorably with those reported for related oxomolybdenum(VI) complexes. The reaction is homogeneous in nature, and a fraction of 2 dissolves and is converted to other types of soluble active species, one of which was isolated and identified as the oxodiperoxo complex [MoO(O2)2(pypzEA)] (3).

The synthesis and crystal structure of a dioxo(μ-oxo)molybdenum(VI) complex of the type [Mo2O4(μ2-O)Cl2(L)2] bearing a bidentate pyrazolylpyridine ligand are described. Catalytic results for the epoxidation of cis-cyclooctene using tert-butylhydroperoxide as oxidant compare favorably with those previously reported for dinuclear oxo-bridged complexes containing different ligands or other complexes bearing the same pyrazolylpyridine ligand.Figure optionsDownload as PowerPoint slide