Table 1. Isotope effects.
| Reaction*
|
|||
|---|---|---|---|
| Rate constant | PCET-N | PCET-P | PCET-S |
| kredKA(H2O), M-1·s-1 | (2.74 ± 0.04) × 101 | (1.48 ± 0.01) × 101 | (6.77 ± 0.01) × 10-1 |
| kredKA(D2O), M-1·s-1† | (6.02 ± 0.03) × 10-2 | (8.30 ± 0.07) × 10-2 | (3.42 ± 0.05) × 10-2 |
| KA(H2O), M-1 | (4.43 ± 0.18) × 103 | (2.15 ± 0.02) × 103 | (1.33 ± 0.10) × 103 |
| KA(D2O), M-1 | (4.28 ± 0.04) × 103 | (2.10 ± 0.02) × 103 | (1.27 ± 0.08) × 103 |
| kred(H2O), s-1 | (6.19 ± 0.05) × 10-3 | (6.94 ± 0.06) × 10-3 | (5.09 ± 0.02) × 10-3 |
| kred(D2O), s-1 | (1.41 ± 0.04) × 10-5 | (3.97 ± 0.05) × 10-5 | (2.69 ± 0.02) × 10-5 |
| kred(H2O)/kred(D2O) | 439 ± 8 | 175 ± 5 | 189 ± 6 |
*
Conditions: 25.0 ± 0.1°C in 1:1 (vol/vol) CH3CN/H2O or 1:1 (vol/vol) CH3CN/D2O.
†
Obtained by extrapolation of plots of kH/kχ versus χD to χD = 1.