INTRINSIC KINETIC SELECTIVITIES IN THE PHOTOOXIDATION OF ORGANIC SUBSTRATES BY A RANGE OF POLYOXOMETALATES VARYING IN REDOX POTENTIAL
Hou, Y; Hill, CL
| HERO ID | 4854515 |
|---|---|
| In Press | No |
| Year | 1992 |
| Title | INTRINSIC KINETIC SELECTIVITIES IN THE PHOTOOXIDATION OF ORGANIC SUBSTRATES BY A RANGE OF POLYOXOMETALATES VARYING IN REDOX POTENTIAL |
| Authors | Hou, Y; Hill, CL |
| Journal | New Journal of Chemistry |
| Volume | 16 |
| Issue | 8-9 |
| Page Numbers | 909-913 |
| Abstract | The data from 4 types of experiments are consistent with radical abstraction, usually rate limiting, as the dominant general mode of reaction of excited state polyoxometalates with organic substrates: (1) the relative rates and quantum yields for oxidation of cyclohexanol by several polyoxometalates varying widely in ground state redox potential from approximately 0V (very irreversible) vs Ag+/Ag in CH3CN for V10O286- to - 1.3 V for W10O324-, (2) the relative reactivities of several cyclohexyl and cyclooctyl derivatives with excited W10O324- and with an authentic ground state organic radical, t-butoxyl, (3) the excellent correlation between the relative rates for reaction of excited W10O324- and cycloalkanes with the C-H bond energies of the substrates, and (4) the product distributions generated on oxidation of five representative substrates by excited W10O324-. The collective data, however, do not rule out other mechanisms for some reactions between excited state polyoxometalates and organic substrates. |
| Wosid | WOS:A1992KC03400012 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |