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Theoretical study on homolytic C(sp2)–O cleavage in ethers and phenols
| Content Provider | Semantic Scholar |
|---|---|
| Author | Ding, Lanlan Zheng, Wenrui Wang, Yingxing |
| Copyright Year | 2015 |
| Abstract | The C–O homolytic bond dissociation enthalpies (BDEs) of many ethers were calculated by high-level ab initio methods including G4, G3, CBS-Q, CBS-4M as well as 26 density function theory (DFT) methods. Among the DFT methods, wB97 provided the most accurate results and the root mean square error (RMSE) is 9.3 kJ mol−1 for 72 C–O BDE calculations. Therefore, extensive C(sp2)–O BDEs and the substituent effect of alkenyl ethers, para-position phenyl ethers/phenols as well as several typical heterocyclic ethers were investigated in detail by wB97 methods, which is important for the understanding of the chemical process involved in the cross-coupling reactions. For alkenyl ethers, the different substituents exhibited significant effects on C(sp2)–O BDEs, especially, the conjugate effect of the substituents on the O atom can greatly decrease the C(sp2)–O BDEs. In addition, the NBO analysis produced good linear correlations between the C(sp2)–O BDEs and qC × qO values (the qC and qO values denoted the natural charge of C and O atoms of the C–O bond, respectively). For para-position phenyl ethers and phenols, excellent linear relationships between the C(sp2)–O BDEs with substituent constant σp+ are found. Further discussion of the substituent effect separated into the ground effect and the radical effect can further help us to understand the essence. For several five-membered typical heterocyclic ethers, a larger bond angle change will lead to a smaller C–O BDE. |
| Starting Page | 6935 |
| Ending Page | 6943 |
| Page Count | 9 |
| File Format | PDF HTM / HTML |
| DOI | 10.1039/C5NJ01354B |
| Alternate Webpage(s) | http://www.rsc.org/suppdata/c5/nj/c5nj01354b/c5nj01354b1.pdf |
| Alternate Webpage(s) | https://pubs.rsc.org/en/content/getauthorversionpdf/C5NJ01354B |
| Alternate Webpage(s) | https://doi.org/10.1039/C5NJ01354B |
| Volume Number | 39 |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
