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Activation and Oxidation of Mesitylene C–H Bonds by (Phebox)Iridium(III) Complexes
| Content Provider | Semantic Scholar |
|---|---|
| Author | Zhou, Meng Johnson, Samantha I. Gao, Yang Emge, Thomas J. Nielsen, Robert J. Goddard, William A. Goldman, Alan S. |
| Copyright Year | 2015 |
| Abstract | A pincer iridium(III) complex, (Phebox)Ir(OAc)2OH2 (1) (Phebox = 3,5-dimethylphenyl-2,6-bis(oxazolinyl)), selectively cleaves the benzylic C–H bond of mesitylene to form an isolable iridium mesityl complex, (Phebox)Ir(mesityl)(OAc) (3), in >90% yield. The trifluoroacetate analogue, (Phebox)Ir(OCOCF3)2OH2 (2), was synthesized to compare with complex 1 for C–H activation, and (Phebox)Ir(mesityl)(OCOCF3) (4) was synthesized by ligand exchange of complex 3. Both complexes 1 and 2 catalyze H/D exchange between mesitylene and D2O at 180 °C, exclusively at the benzylic position; 2 gave a higher turnover number (11 TO) than 1 (6 TO) in 12 h. Using d4-acetic acid as the source of deuterium, up to 92 turnovers of benzylic H/D exchange of mesitylene were obtained with complex 1. (Phebox)Ir(OCOCF3)2OH2 catalyzed the benzylic C–H oxidation of mesitylene using Ag2O as a terminal oxidant at 130 °C, to form 3,5-dimethylbenzaldehyde and 3,5-dimethylbenzoic acid in 35% ± 4% yield (5.1 ± 0.6 TO). DFT calculations were used ... |
| Starting Page | 2879 |
| Ending Page | 2888 |
| Page Count | 10 |
| File Format | PDF HTM / HTML |
| DOI | 10.1021/acs.organomet.5b00200 |
| Volume Number | 34 |
| Alternate Webpage(s) | http://www.wag.caltech.edu/publications/sup/pdf/1124.pdf |
| Alternate Webpage(s) | https://doi.org/10.1021/acs.organomet.5b00200 |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
