Table 4.
Measured (exp) and Predicted (calcd) Thermodynamic Parameters for the Reactions of the Indicated Complexes with DHA and DHA-d4 in CH2Cl2a
| LCuOH (1a)
|
NO2LCuOH (3)
|
pipMeLCuOH (4b)
|
||||
|---|---|---|---|---|---|---|
| exp | calcdb | exp | calcdb | exp | calcdb | |
| ΔH‡H | 5.1(1) | 5.1 | 4.9(1) | 4.2 | 3.8(2) | 5.5 |
| ΔH‡D | 5.5(3) | 6.4 | 8.5(3) | 5.9 | 6.7(3) | 6.8 |
| ΔH‡D − ΔH‡H | 0.4(2) | 1.3 | 3.6(3) | 1.7 | 2.9(4) | 1.3 |
| ΔS‡H | −31(3) | −31.7 | −27(1) | −25.7 | −38(3) | −32.2 |
| ΔS‡D | −36(4) | −34.3 | −17(1) | −24.6 | −32(4) | −34.8 |
| ΔS‡D − ΔS‡H | −5(5) | −2.6 | 10(1.4) | 1.1 | 6(5) | −2.6 |
| KIE (−80 °C)c | 35 | 82 | 77 | 38 | 93 | 86 |
| KIE (−40 °C) | 29 | 64 | 26 | 25 | 25 | 66 |
| KIE (25 °C)c | 24 | 29 | 2.8 | 11 | 6.5 | 30 |
a
ΔH‡ values in kcal mol−1; ΔS‡ in eu (cal mol−1 K−1). The temperature range for reactions with DHA and DHA-d4 in CH2Cl2 were −40°C to −80°C and −20 °C to −50 °C, respectively.
b
See SI for full details on computed rate constants and derived activation parameters.
c
Extrapolated values, determined from activation parameters.