A Dinuclear Oxoperoxomolybdenum(VI) Complex, [Mo₂O₆(OH)₂(Pyridine Oxide Tetrazolate)₂], Displaying the {MoO(O₂)(<i>μ</i>‐OH)₂MoO(O₂)}⁰ Core, and its Catalytic Per

The dinuclear oxoperoxomolybdenum(VI) complex [Mo 2 O 6 (OH) 2 (pto) 2 ] ( 1 ), containing a rare example of a hydroxo‐bridged {MoO(O 2 )( μ ‐OH) 2 MoO(O 2 )} 0 core, has been synthesized via the reaction of MoO 3 with H 2 O 2 and 5‐(2‐pyridyl‐1‐oxide)tetrazole (Hpto) and characterized by elemental analysis and ICP‐OES, infrared and Raman spectroscopies, single crystal X‐ray diffraction, nuclear magnetic resonance, and mass spectrometry. Compound 1 is an effective homogeneous catalyst for olefin epoxidation. The type of oxidant, namely tert ‐butyl hydroperoxide (TBHP) or H 2 O 2 , influences the catalytic performance. For cis ‐cyclooctene epoxidation, 1 /TBHP led to 100% conversion after 4 h at 70 °C, and 1 /H 2 O 2 led to 80% conversion after 24 h at 70 °C. Catalyst recycling is feasible using an ionic liquid solvent with high affinity for the catalyst, and product separation via an extraction process. The catalytic potential of 1 was further explored for the chemical valorization of biomass‐derived fatty acid methyl esters (FAMEs), namely C18‐unsaturated methyl oleate and methyl linoleate derived from vegetable oils. The reaction of FAMEs/TBHP gave mainly epoxidized FAMEs (&gt;97% selectivity at high conversions of 97–100%, at 70 °C). This catalyst is a rare example of a dinuclear organo‐oxomolybdenum(VI) compound with the ability to epoxidize FAMEs.