Mulliken spin populations on key atoms of side chain analogs of the redox-active side chain in 2MP-α3C and 4MP-α3C calculated with CASSCF/aug-cc-pVTPZ.
| System | Atoma | Total Sb | ||
|---|---|---|---|---|
| O | S | S2 | ||
| Y–O˙ | 0.340 | — | — | — |
| 2MP-O˙ | 0.310 | 0.013 | 0.006 | 0.019 |
| 4MP-O˙ | 0.321 | 0.049 | 0.002 | 0.051 |
| Y–OH+˙ | 0.106 | — | — | — |
| 2MP-OH+˙ | 0.120 | 0.105 | 0.003 | 0.108 |
| 4MP-OH+˙ | 0.041 | 0.453 | 0.078 | 0.531 |
a
O refers to the hydroxyl oxygen of the sidechain, S refers to the sulfur atom closest to the phenol ring, and S2 refers to the sulfur atom most distal to the phenol ring, i.e., closest to the backbone.
b
“Total S” refers to the total spin population on the sulfur atoms in the molecule. A full set of data is available in the ESI for all theoretical methods used in this study.