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Cyclopentadienyl molybdenum alkyl ester complexes as catalyst precursors for olefin epoxidation
| Content Provider | Semantic Scholar |
|---|---|
| Author | Grover, Nidhi Pöthig, Alexander Kühn, Fritz E. |
| Copyright Year | 2014 |
| Abstract | 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. |
| Starting Page | 4219 |
| Ending Page | 4231 |
| Page Count | 13 |
| File Format | PDF HTM / HTML |
| DOI | 10.1039/C4CY00738G |
| Alternate Webpage(s) | https://pubs.rsc.org/en/content/getauthorversionpdf/C4CY00738G |
| Alternate Webpage(s) | http://www.rsc.org/suppdata/cy/c4/c4cy00738g/c4cy00738g1.pdf |
| Alternate Webpage(s) | https://mediatum.ub.tum.de/doc/1315798/1315798.pdf |
| Alternate Webpage(s) | https://pubs.rsc.org/en/content/articlepdf/2014/cy/c4cy00738g |
| Alternate Webpage(s) | https://doi.org/10.1039/C4CY00738G |
| Volume Number | 4 |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
