875148-65-5Relevant articles and documents
Cyclopentadienyl molybdenum alkyl ester complexes as catalyst precursors for olefin epoxidation
Grover, Nidhi,P?thig, Alexander,Kühn, Fritz E.
, p. 4219 - 4231 (2014)
New molybdenum complexes of the type [CpMo(CO)3X] containing ligands of the formula X = CHR2CO(OR1) where R1 = ethyl (1), menthyl (4), and bornyl (5) and R2 = H; R1 = ethyl and R2 = methyl (2) and phenyl (3) have been synthesized and characterized by NMR and IR spectroscopy and X-ray crystallography. These compounds have been applied as catalyst precursors for achiral and chiral epoxidation of unfunctionalized olefins with tert-butyl hydroperoxide (TBHP) as the oxidant at 22 °C (in CH2Cl2) and 55°C (in CHCl3). The substrates cis-cyclooctene, 1-octene, cis- and trans-stilbene, and trans-β-methylstyrene were selectively and quantitatively converted into their epoxides using a catalyst:substrate:oxidant ratio of 1:100:200 within 4 h at room temperature in CH2Cl2 and within 15 min at 55°C in CHCl3. Complexes 1-5 are precursors of active epoxidation catalysts and turnover frequencies (TOFs) of ca. 1200 h-1 are obtained with cis-cyclooctene as the substrate. No enantioselectivity is observed with trans-β-methylstyrene as the substrate despite the application of enantiomerically pure precatalysts. In situ monitoring of catalytic epoxidation of cis-cyclooctene with complex 5 by 1H and 13C NMR spectroscopy suggests that the chiral alkyl ester side chain is retained during oxidation with TBHP. During epoxidation, the primary catalytic species is the dioxo complex [CpMoO2X]. After near complete conversion of cis-cyclooctene to its epoxide, further oxidation of the dioxo complex to oxo-peroxo complex [CpMo(η2-O2)(O)X] takes place. The oxo-peroxo complex is also an active epoxidation catalyst.
