| Autor: |
McKee ML; Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama36849, United States. |
| Jazyk: |
angličtina |
| Zdroj: |
The journal of physical chemistry. A [J Phys Chem A] 2022 Aug 04; Vol. 126 (30), pp. 4969-4980. Date of Electronic Publication: 2022 Jul 21. |
| DOI: |
10.1021/acs.jpca.2c03344 |
| Abstrakt: |
The mechanism of C-H oxidation of propylene (C 3 H 6 ) and 1-phenyl-1-pentyne (C 3 H 7 -C≡C-Ph) by HOOR (R═Me, t Bu) and 3 O 2 by a copper-salen complex was explored by computations. The most noteworthy step is the complexation of two Cu salens to the peroxide to form either the LCuOH/LCuOR pair or an OH-bridged complex LCu(μ-OH)CuL plus OR. The latter pathway involves an avoided crossing of two triplet electronic states. The LCuOH complex can abstract a hydrogen atom from C 3 H 6 and the C 3 H 5 radical plus 3 O 2 forms the complex LCuOOC 3 H 5 . Migration of a hydrogen to the proximal oxygen atom reforms LCuOH and acrolein HC(O)CH═CH 2 . |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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