Table 6. Reduction Potentials (E°, V) Computed for RO(H)-Bound States. When Applicable, Redox Potentials Coupled to Proton Transfer (E°′, V) Are Indicated in Parentheses.
| state | DFT/COSMO | DFT/SCRF |
|---|---|---|
| RO–P–EH(RO–) | –2.39 | –1.86 (−1.29)a |
| RO–PHEH(RO–) | –2.14 (−1.42) | –1.64 (−1.19)c |
| ROHP–E–(ROH) | –1.82 | –1.47 (−1.29)b |
| ROHPHE–(ROH) | –1.44 | –1.03 |
| ROHP–EH(ROH) | –1.52 | –1.07 (−1.06)c |
| ROHPHEH(ROH) | –1.42 | –0.91c |
a
Electron transfer accompanies proton addition and a proton shift to generate the ROHPHE–(ROH) 1e– reduced state.
b
Electron transfer accompanies proton addition to generate the ROHPHEH(ROH) 1e– reduced state.
c
Electron transfer accompanies an internal proton transfer to generate the ROHPHE–(ROH) 1e– reduced state.