Singly Unified Driving Force Dependence of Outer-Sphere Electron-Transfer Pathways of Nonheme Manganese(IV)-Oxo Complexes in the Absence and Presence of Lewis Acids
Sharma, N; Lee, YM; Li, XX; Nam, W; Fukuzumi, S
| HERO ID | 5929800 |
|---|---|
| In Press | No |
| Year | 2019 |
| Title | Singly Unified Driving Force Dependence of Outer-Sphere Electron-Transfer Pathways of Nonheme Manganese(IV)-Oxo Complexes in the Absence and Presence of Lewis Acids |
| Authors | Sharma, N; Lee, YM; Li, XX; Nam, W; Fukuzumi, S |
| Journal | Inorganic Chemistry |
| Volume | 58 |
| Issue | 20 |
| Page Numbers | 13761-13765 |
| Abstract | Epoxidation of styrene derivatives, sulfoxidation of thioanisole derivatives, and hydroxylation of toluene derivatives by a nonheme manganese(IV)-oxo complex binding triflic acid, [(N4Py)MnIV(O)]2+-(HOTf)2 [1-(H+)2], and scandium triflate, [(N4Py)MnIV(O)]2+-(Sc(OTf)3)2 [1-(Sc3+)2], occur via outer-sphere electron-transfer (OSET) pathways, exhibiting singly unified driving force dependence, enabling one to predict absolute values of the second-order rate constants of these three types of substrate oxidations by the manganese(IV)-oxo complex, using the Marcus theory of electron transfer. When [(N4Py)MnIV(O)]2+ (1) was replaced by [(N4Py)FeIV(O)]2+ (2), OSET pathways were changed to inner-sphere electron-transfer (ISET) pathways. The difference in the OSET versus ISET pathways is clarified based on the difference in the Lewis basicity of the oxo moieties in 1 and 2. |
| Doi | 10.1021/acs.inorgchem.9b02403 |
| Pmid | 31589029 |
| Wosid | WOS:000492117900025 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |
| Language Text | English |