Dimeric μ-oxo bridged molybdenum(VI) dioxo complexes as catalysts in the epoxidation of internal and terminal alkenes

The preparation of the tridentate phenol based amine ligands HL1-HL4 is achieved via a convenient one-pot synthesis by reductive amination in quantitative yield in an autoclave under 7 bar H-2 gas. Reaction of [MoO2(acac)(2)] and the corresponding ligand HLX (X = 1, 2 and 4) in methanol-H2O results in the formation of orange to red dimeric mu-oxo bridged [{MoO2(LX)}(2)(mu-O)] (X = 1, 2 and 4) complexes 1-3 in high yield and high purity. Complexes 1-3 are stable towards air and water. Both ligands coordinate via the phenolic O atom, the amine N atom and the third donor atom in the side chain (OMe for 1 and NMe2 for 2 and 3) in a fac mode to the metal center. The molybdenum atoms are linked by a bridging mu-oxo moiety to each other as confirmed by X-ray diffraction analyses of complexes 2 and 3. All complexes have been tested in the epoxidation of several internal and terminal alkenes using TBHP as an oxidant. Depending on the nature of the substrate, the epoxides are obtained in moderate to good yields and high selectivities. In the epoxidation of cyclooctene a TOF = 467 h(-1) with complex 1 has been observed, significantly higher compared to other dimeric complexes reported in the literature. In the more challenging epoxidation of styrene, complexes 1 and 2 have proven to be highly selective as only the formation of styrene oxide is observed. The OMe based complex 1 has also proven to be more active than the NMe2 based counterparts 2 and 3. The basic conditions induced by the NMe2 groups in complexes 2 and 3 lower their catalytic activity.